Pyrazole tetrahydronaphthyl carboxamides

ABSTRACT

The present invention relates to novel pyrazole(thio)tetrahydronaphthyl carboxamides, to processes for preparing these compounds, to compositions comprising these compounds, and to the use thereof as biologically active compounds, especially for control of harmful microorganisms in crop protection and in the protection of materials.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser.No. 14/399,544, filed Nov. 7, 2014, which is a §371 National Stageapplication of PCT/EP2013/059414, filed May 6, 2013, which claimspriority to European Application No. 12167286.9, filed May 9, 2012, andEuropean Application No. 12197383.8, filed Dec. 16, 2012, the contentsof which are incorporated herein by reference in their entireties.

BACKGROUND

1. Field of the Invention

The present invention relates to novel pyrazole(thio)tetrahydronaphthylcarboxamides, to processes for preparing these compounds, tocompositions comprising these compounds, and to the use thereof asbiologically active compounds, especially for control of harmfulmicroorganisms in crop protection and in the protection of materials.

2. Description of Related Art

It is already known that certain pyrazole tetrahydronaphthyl, but nottetrahydronaphthyl, carboxamides have fungicidal properties (e.g. WO92/12970, EP-A 0 199 822, EP-A 0 276 177, JP-A 62-096472, JP-A05-310512, JP-A 01-313402, WO 02/059086, WO 2004/103975 and J. Org.Chem. 1995, 60, 1626-1631).

Since the ecological and economic demands made on modern activeingredients, for example fungicides, are increasing constantly, forexample with respect to activity spectrum, toxicity, selectivity,application rate, formation of residues and favourable manufacture, andthere can also be problems, for example, with resistances, there is aconstant need to develop novel fungicidal compositions which haveadvantages over the known compositions at least in some areas.

SUMMARY

This invention now provides novel1-methyl-3-dihalogenomethyl-5-halogenopyrazole(thio)tetrahydronaphthylcarboxamides of the formula (I)

in which

-   Hal¹ represents chlorine or fluorine;-   Hal² represents chlorine or fluorine;-   T represents an oxygen or sulfur atom;-   Q represents hydrogen, C₁-C₆-alkylsulfonyl,    C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkylsulfonyl,    halo-C₁-C₄-alkoxy-C₁-C₄-alkyl;-   X represents halogen, nitro, cyano, C₁-C₁₂-alkyl; C₁-C₆-haloalkyl    having 1 to 9 identical or different halogen atoms; C₁-C₆-alkoxy;    C₁-C₆-haloalkoxy having 1 to 9 identical or different halogen atoms;    C₁-C₆-alkylsulfanyl; C₁-C₆-haloalkylsulfanyl having 1 to 9 identical    or different halogen atoms; C₁-C₆-alkylsulfonyl;    C₁-C₆-haloalkylsulfonyl having 1 to 9 identical or different halogen    atoms; C₂-C₁₂-alkenyl; C₂-C₁₂-alkynyl; C₃-C₇-cycloalkyl; phenyl;    tri(C₁-C₈)alkylsilyl; tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl;-   m represents 0, 1, 2 or 3-   R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independently one to another    represent hydrogen; halogen; cyano; C₁-C₁₆-alkyl; C₂-C₁₆-haloalkyl    having 1 to 9 identical or different halogen atoms;    C₃-C₈-cycloalkyl; C₃-C₇-halocycloalkyl having 1 to 9 identical or    different halogen atoms; C₁-C₆-haloalkyl having 1 to 9 identical or    different halogen atoms; (C₃-C₈-cycloalkyl)-C₁-C₈-alkyl;    (C₃-C₈-cycloalkyl)-C₃-C₈-cycloalkyl; C₂-C₁₆-alkenyl; C₂-C₁₆-alkynyl;    C₂-C₁₆-alkenyl-C₁-C₁₆-alkyl; C₂-C₁₆-alkynyl-C₁-C₁₆-alkyl;    C₁-C₁₆-alkoxy; C₃-C₈-cycloalkyloxy;    (C₃-C₈-cycloalkyl)-C₁-C₈-alkyloxy; C₁-C₈-alkylsulfanyl;    C₃-C₈-cycloalkylsulfanyl; (C₃-C₈-cycloalkyl)-C₁-C₈-alkylsulfanyl;    C₂-C₁₆-alkenyloxy; C₃-C₈-alkynyloxy; aryl-C₁-C₈-alkyloxy which is    optionally substituted by up to 6 identical or different groups    R^(b); aryl-C₁-C₈-alkylsulfanyl which is optionally substituted by    up to 6 identical or different groups R^(b); aryloxy which is    optionally substituted by up to 6 identical or different groups    R^(b); arylsulfanyl which is optionally substituted by up to 6    identical or different groups R^(b);    (C₃-C₈-cycloalkyl)-C₂-C₈-alkenyl; (C₃-C₈-cycloalkyl)-C₂-C₈-alkynyl;    tri(C₁-C₈)alkylsilyl; tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl;    aryl-C₁-C₈-alkyl which is optionally substituted by up to 6    identical or different groups R^(b); aryl-C₂-C₈-alkenyl which is    optionally substituted by up to 6 identical or different groups    R^(b); aryl-C₂-C₈-alkynyl which is optionally substituted by up to 6    identical or different groups R^(b); C₁-C₈-alkylamino;    di-C₁-C₈-alkylamino; arylamino which is optionally substituted by up    to 6 identical or different groups R^(b); C₁-C₈-alkylcarbonyl;    C₁-C₈-alkylcarbonyloxy; C₁-C₈-alkylcarbonylamino;    C₁-C₈-alkoxycarbonyl; C₁-C₈-alkyloxycarbonyloxy;    C₁-C₈-alkylcarbamoyl; di-C₁-C₈-alkylcarbamoyl;    C₁-C₈-alkylaminocarbonyloxy; di-C₁-C₈-alkylaminocarbonyloxy;    N—(C₁-C₈-alkyl)hydroxycarbamoyl; C₁-C₈-alkoxycarbamoyl;    N—(C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl; aryl-C₁-C₈-alkylamino which    is optionally substituted by up to 6 identical or different groups    R^(b); (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;    (C₂-C₈-cycloalkoxyimino)-C₁-C₈-alkyl; C₁-C₈-alkyliminoxy;    C₁-C₈-alkyliminoxy-C₁-C₈-alkyl; each of which is optionally    substituted;    -   provided that R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ do not represent        hydrogen at the same time when R⁸ represents hydrogen or        trifluoromethyl;-   R¹ and R² can form together with the carbon to which they are    attached a C₃-C₈-cycloalkyl; C₃-C₈-cycloalkenyl, or a saturated 5, 6    or 7 membered heterocycle; each of which is optionally substituted;    or may represent a group ═C(Y¹)Y² or a group ═N—O—R^(c);-   R³ and R⁴ can form together with the carbon to which they are    attached a C₃-C₈-cycloalkyl; C₃-C₈-cycloalkenyl, or a saturated 5, 6    or 7 membered heterocycle; each of which is optionally substituted;    or may represent a group ═C(Y¹)Y² or a group ═N—O—R^(c);-   R⁵ and R⁶ can form together with the carbon to which they are    attached a C₃-C₈-cycloalkyl; C₃-C₈-cycloalkenyl, or a saturated 5, 6    or 7 membered heterocycle; each of which is optionally substituted;    or may represent a group ═C(Y¹)Y² or a group ═N—O—R^(c);-   R⁷ and R⁸ can form together with the carbon to which they are    attached a C₃-C₈-cycloalkyl; C₃-C₈-cycloalkenyl, or a saturated 5, 6    or 7 membered heterocycle; each of which is optionally substituted;    or may represent a group ═C(Y¹)Y² or a group ═N—O—R^(c);-   R¹ and R³ or R³ and R⁵ or R⁵ and R⁷ can form with the carbons to    which they are attached a C₃-C₈-cycloalkyl; C₃-C₈-cycloalkenyl, or a    saturated 5, 6 or 7 membered heterocycle; each of which is    optionally substituted;-   R^(b) represents halogen; nitro, cyano, C₁-C₆-haloalkyl having 1 to    9 identical or different halogen atoms; C₁-C₆-alkoxy;    C₁-C₆-haloalkoxy having 1 to 9 identical or different halogen atoms;    C₁-C₆-alkylsulfanyl; C₁-C₆-haloalkylsulfanyl having 1 to 9 identical    or different halogen atoms; C₁-C₆-alkylsulfonyl;    C₁-C₆-haloalkylsulfonyl having 1 to 9 identical or different halogen    atoms; C₂-C₁₂-alkenyl; C₂-C₁₂-alkynyl; C₃-C₇-cycloalkyl; phenyl;    tri(C₁-C₈)alkylsilyl; tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl;-   Y¹ and Y² independently of one another represent hydrogen, halogen,    C₁-C₁₂-alkyl; C₁-C₆-haloalkyl having 1 to 9 identical or different    halogen atoms; C₁-C₈-alkylsulfanyl; phenyl; each of which is    optionally substituted; or Y¹ and Y² can form together with the    carbon to which they are attached a C₃-C₈-cycloalkyl or a    C₃-C₈-cycloalkenyl or a saturated 5, 6 or 7 membered heterocycle;    each of which is optionally substituted;-   R^(c) represents C₁-C₁₆-alkyl; C₁-C₆-haloalkyl having 1 to 9    identical or different halogen atoms; C₃-C₈-cycloalkyl;    (C₃-C₈-cycloalkyl)-C₁-C₈-alkyl; (C₃-C₈-cycloalkyl)-C₃-C₈-cycloalkyl;    C₂-C₈-alkenyl-C₁-C₁₆-alkyl; C₂-C₈-alkynyl-C₁-C₁₆-alkyl;    aryl-C₁-C₈-alkyl which is optionally substituted by up to 6    identical or different groups R^(b); each of which is optionally    substituted.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

In a preferred embodiment1-methyl-3-dihalogenomethyl-5-halogenopyrazole(thio)tetrahydronaphthylcarboxamides of formula (I) are described, wherein

-   -   Hal¹ represents chlorine or fluorine;    -   Hal² represents chlorine or fluorine;    -   T represents an oxygen atom;    -   Q represents hydrogen, C₁-C₄-alkylsulfonyl,        C₁-C₃-alkoxy-C₁-C₃-alkyl, C₁-C₄-haloalkylsulfonyl,        halo-C₁-C₃-alkoxy-C₁-C₃-alkyl having in each case 1 to 9        fluorine, chlorine and/or bromine atoms;    -   X represents fluorine, chlorine, methyl or trifluoromethyl;    -   m represents 0, 1 or 2;    -   R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independently one to another        represent hydrogen, halogen; cyano; C₁-C₁₆-alkyl;        C₁-C₆-haloalkyl having 1 to 9 identical or different halogen        atoms; C₃-C₈-cycloalkyl; (C₃-C₈-cycloalkyl)-C₁-C₈-alkyl;        (C₃-C₈-cycloalkyl)-C₃-C₈-cycloalkyl; C₂-C₈-alkenyl;        C₂-C₈-alkynyl; C₂-C₈-alkenyl-C₁-C₁₆-alkyl;        C₂-C₈-alkynyl-C₁-C₁₆-alkyl; C₁-C₁₆-alkoxy; C₃-C₈-cycloalkyloxy;        (C₃-C₈-cycloalkyl)-C₁-C₈-alkyloxy; C₁-C₈-alkylsulfanyl;        C₃-C₈-cycloalkylsulfanyl;        (C₃-C₈-cycloalkyl)-C₁-C₈-alkylsulfanyl; C₂-C₈-alkenyloxy;        C₃-C₈-alkynyloxy; aryl-C₁-C₈-alkyloxy which is optionally        substituted by up to 6 identical or different groups R^(b);        aryl-C₁-C₈-alkylsulfanyl which is optionally substituted by up        to 6 identical or different groups R^(b); aryloxy which is        optionally substituted by up to 6 identical or different groups        R^(b); arylsulfanyl which is optionally substituted by up to 6        identical or different groups R^(b);        (C₃-C₈-cycloalkyl)-C₂-C₈-alkenyl;        (C₃-C₈-cycloalkyl)-C₂-C₈-alkynyl; tri(C₁-C₈)alkylsilyl;        tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl; aryl-C₁-C₈-alkyl which is        optionally substituted by up to 6 identical or different groups        R^(b); aryl-C₂-C₈-alkenyl which is optionally substituted by up        to 6 identical or different groups R^(b); aryl-C₂-C₈-alkynyl        which is optionally substituted by up to 6 identical or        different groups R^(b); each of which is optionally substituted;        provided that R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ do not represent        hydrogen at the same time when R⁸ represents hydrogen or        trifluoromethyl;    -   to R¹ and R² can form together with the carbon to which they are        attached an optionally substituted C₃-C₈-cycloalkyl; or may form        the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another        represent hydrogen, halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl        having 1 to 9 identical or different halogen atoms or form        together with the carbon to which they are attached an        optionally substituted cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl) or a group ═N—O—R^(c) (where R^(c) represents        C₁-C₁₂-alkyl; C₁-C₆-haloalkyl having 1 to 9 identical or        different halogen atoms; C₃-C₆-cycloalkyl;        (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;        (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;        C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally        substituted by up to 6 identical or different groups R^(b); each        of which is optionally substituted);    -   R³ and R⁴ can form together with the carbon to which they are        attached an optionally substituted C₃-C₈-cycloalkyl; or may form        the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another        represent hydrogen, halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl        having 1 to 9 identical or different halogen atoms or form        together with the carbon to which they are attached an        optionally substituted cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl) or a group ═N—O—R^(c) (where R^(c) represents        C₁-C₁₂-alkyl; C₁-C₆-haloalkyl having 1 to 9 identical or        different halogen atoms; C₃-C₆-cycloalkyl;        (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;        (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;        C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally        substituted by up to 6 identical or different groups R^(b); each        of which is optionally substituted);    -   R⁵ and R⁶ can form together with the carbon to which they are        attached an optionally substituted C₃-C₈-cycloalkyl; or may form        the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another        represent hydrogen, halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl        having 1 to 9 identical or different halogen atoms or form        together with the carbon to which they are attached an        optionally substituted cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl) or a group ═N—O—R^(c) (where R^(c) represents        C₁-C₁₂-alkyl; C₁-C₆-haloalkyl having 1 to 9 identical or        different halogen atoms; C₃-C₆-cycloalkyl;        (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;        (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;        C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally        substituted by up to 6 identical or different groups R^(b); each        of which is optionally substituted);    -   R⁷ and R⁸ can form together with the carbon to which they are        attached an optionally substituted C₃-C₈-cycloalkyl; or may form        the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another        represent hydrogen, halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl        having 1 to 9 identical or different halogen atoms or form        together with the carbon to which they are attached an        optionally substituted cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl) or a group ═N—O—R^(c) (where R^(c) represents        C₁-C₁₂-alkyl; C₁-C₆-haloalkyl having 1 to 9 identical or        different halogen atoms; C₃-C₆-cycloalkyl;        (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;        (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;        C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally        substituted by up to 6 identical or different groups R^(b); each        of which is optionally substituted);

R¹ and R³ or R³ and R⁵ or R⁵ and R⁷ can form with the carbons to whichthey are attached an optionally substituted C₃-C₈-cycloalkyl;

-   -   R^(b) represents halogen; nitro, cyano, C₁-C₈-alkyl;        C₁-C₄-haloalkyl having 1 to 9 identical or different halogen        atoms; C₁-C₆-alkoxy; C₁-C₄-haloalkoxy having 1 to 9 identical or        different halogen atoms; C₁-C₆-alkylsulfanyl;        C₁-C₄-haloalkylsulfanyl having 1 to 9 identical or different        halogen atoms; C₁-C₆-alkylsulfonyl; C₁-C₄-haloalkylsulfonyl        having 1 to 9 identical or different halogen atoms;        C₂-C₈-alkenyl; C₂-C₈-alkynyl; C₃-C₆-cycloalkyl; phenyl;        tri(C₁-C₆)alkylsilyl; tri(C₁-C₆)alkylsilyl-C₁-C₆-alkyl.

In a very preferred embodiment1-Methyl-3-dihalogenomethyl-5-halogenopyrazole(thio)tetrahydronaphthylcarboxamides of formula (I) are described, wherein

-   Hal¹ represents chlorine or fluorine;-   Hal² represents chlorine or fluorine;-   T represents an oxygen atom;-   Q represents hydrogen, methylsulfonyl, ethylsulfonyl, n- or    isopropylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl,    methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl,    trifluoromethylsulfonyl, trifluoromethoxymethyl;-   X represents fluorine, chlorine, methyl or trifluoromethyl located    in the 4-, 5- or 6-position;-   m represents 0 or 1;-   R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independently of one another    represent hydrogen, fluorine, chlorine, bromine, iodine;    C₁-C₁₂-alkyl; C₁-C₆-haloalkyl having 1 to 9 identical or different    halogen atoms; C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;    (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₁-C₁₂-alkoxy;    C₃-C₆-cycloalkyloxy; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyloxy; each of    which is optionally substituted; provided that R¹, R², R³, R⁴, R⁵,    R⁶ and R⁷ do not represent hydrogen at the same time when R⁸    represents hydrogen or trifluoromethyl;-   R¹ and R² can form together with the carbon to which they are    attached an optionally substituted cyclopropyl, cyclobutyl,    cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y² (where Y¹    and Y² independently of one another represent hydrogen, fluorine,    chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl; C₁-C₄-haloalkyl    having 1 to 9 identical or different fluorine, chlorine or bromine    atoms; C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl;    C₂-C₆-alkenyl-C₁-C₈-alkyl; C₂-C₆-alkynyl-C₁-C₈-alkyl;    aryl-C₁-C₄-alkyl which is optionally substituted by up to 5    identical or different groups R^(b); each of which is optionally    substituted);-   R³ and R⁴ can form together with the carbon to which they are    attached an optionally substituted cyclopropyl, cyclobutyl,    cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y² (where Y¹    and Y² independently of one another represent hydrogen, fluorine,    chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl; C₁-C₄-haloalkyl    having 1 to 9 identical or different fluorine, chlorine or bromine    atoms; C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl;    C₂-C₆-alkenyl-C₁-C₈-alkyl; C₂-C₆-alkynyl-C₁-C₈-alkyl;    aryl-C₁-C₄-alkyl which is optionally substituted by up to 5    identical or different groups R^(b); each of which is optionally    substituted);-   R⁵ and R⁶ can form together with the carbon to which they are    attached an optionally substituted cyclopropyl, cyclobutyl,    cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y² (where Y¹    and Y² independently of one another represent fluorine, chlorine,    bromine, methyl; ethyl, propyl, isopropyl) or a group ═N—O—R^(c)    (where R^(c) represents C₁-C₈-alkyl; C₁-C₄-haloalkyl having 1 to 9    identical or different fluorine, chlorine or bromine atoms;    C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl;    C₂-C₆-alkenyl-C₁-C₈-alkyl; C₂-C₆-alkynyl-C₁-C₈-alkyl;    aryl-C₁-C₄-alkyl which is optionally substituted by up to 5    identical or different groups R^(b); each of which is optionally    substituted);-   R⁷ and R⁸ can form together with the carbon to which they are    attached an optionally substituted cyclopropyl, cyclobutyl,    cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y² (where Y¹    and Y² independently of one another represent hydrogen, fluorine,    chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl; C₁-C₄-haloalkyl    having 1 to 9 identical or different fluorine, chlorine or bromine    atoms; C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl;    C₂-C₆-alkenyl-C₁-C₈-alkyl; C₂-C₆-alkynyl-C₁-C₈-alkyl;    aryl-C₁-C₄-alkyl which is optionally substituted by up to 5    identical or different groups R^(b); each of which is optionally    substituted);-   R¹ and R³ or R³ and R⁵ or R⁵ and R⁷ can form together with the    carbons to which they are attached an optionally substituted    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.-   R^(b) represents fluorine, chlorine, bromine; C₁-C₆-alkyl;    C₁-C₄-haloalkyl having 1 to 9 identical or different halogen atoms;    C₁-C₄-alkoxy; C₁-C₄-haloalkoxy having 1 to 9 identical or different    halogen atoms; C₁-C₄-alkylsulfanyl; C₁-C₄-haloalkylsulfanyl having 1    to 9 identical or different halogen atoms; C₁-C₄-alkylsulfonyl;    C₁-C₄-haloalkylsulfonyl having 1 to 9 identical or different halogen    atoms; C₂-C₆-alkenyl; C₂-C₆-alkynyl; C₃-C₆-cycloalkyl; phenyl;    tri(C₁-C₄)alkylsilyl; tri(C₁-C₄)alkylsilyl C₁-C₄ alkyl.

The formula (I) provides a general definition of the1-methyl-3-dihalogenomethyl-5-halogenopyrazole(thio)tetrahydronaphthylcarboxamides according to the invention. Preferred radical definitionsfor the formulae shown above and below are given below. Thesedefinitions apply to the end products of the formula (I) and likewise toall intermediates.

-   Hal¹ preferably represents chlorine.-   Hal¹ also preferably represents fluorine.-   Hal² preferably represents chlorine.-   Hal² also preferably represents fluorine.-   T preferably represents an oxygen atom.-   Q preferably represents hydrogen, C₁-C₄-alkylsulfonyl,    C₁-C₃-alkoxy-C₁-C₃-alkyl, C₁-C₄-haloalkylsulfonyl,    halo-C₁-C₃-alkoxy-C₁-C₃-alkyl having in each case 1 to 9 fluorine,    chlorine and/or bromine atoms;-   Q particularly preferably represents hydrogen, methylsulfonyl,    ethylsulfonyl, n- or isopropylsulfonyl, n-, iso-, sec- or    tert-butylsulfonyl, methoxymethyl, methoxyethyl, ethoxymethyl,    ethoxyethyl, trifluoromethylsulfonyl, trifluoromethoxymethyl.-   Q very particularly preferably represents hydrogen.-   X preferably represents fluorine, chlorine, methyl or    trifluoromethyl.-   X particularly preferably represents fluorine, where fluorine is    particularly preferably located in the 4-, 5- or 6-position, very    particularly preferably in the 4- or 6-position, in particular in    the 4-position of the tetrahydronaphthyl radical.-   X moreover particularly preferably represents chlorine, where    chlorine is particularly preferably located in the 4- or 5-position,    in particular in the 4-position of the tetrahydronaphthyl radical.-   X moreover particularly preferably represents methyl, where methyl    is particularly preferably located in the 4- or 5-position of the    tetrahydronaphthyl radical.-   X moreover particularly preferably represents trifluoromethyl, where    trifluoromethyl is particularly preferably located in the 4- or    5-position of the tetrahydronaphthyl radical.-   m preferably represents 0, 1 or 2.-   m particularly preferably represents 0 or 1.-   m very particularly preferably represents 0.-   R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independently of one another    preferably represent hydrogen, halogen; cyano; C₁-C₁₆-alkyl;    C₁-C₆-haloalkyl having 1 to 9 identical or different halogen atoms;    C₃-C₈-cycloalkyl; (C₃-C₈-cycloalkyl)-C₁-C₈-alkyl;    (C₃-C₈-cycloalkyl)-C₃-C₈-cycloalkyl; C₂-C₈-alkenyl; C₂-C₈-alkynyl;    C₂-C₈-alkenyl-C₁-C₁₆-alkyl; C₂-C₈-alkynyl-C₁-C₁₆-alkyl;    C₁-C₁₆-alkoxy; C₃-C₈-cycloalkyloxy;    (C₃-C₈-cycloalkyl)-C₁-C₈-alkyloxy; C₁-C₈-alkylsulfanyl;    C₃-C₈-cycloalkylsulfanyl; (C₃-C₈-cycloalkyl)-C₁-C₈-alkylsulfanyl;    C₂-C₈-alkenyloxy; C₃-C₈-alkynyloxy; aryl-C₁-C₈-alkyloxy which is    optionally substituted by up to 6 identical or different groups    R^(b); aryl-C₁-C₈-alkylsulfanyl which is optionally substituted by    up to 6 identical or different groups R^(b); aryloxy which is    optionally substituted by up to 6 identical or different groups    R^(b); arylsulfanyl which is optionally substituted by up to 6    identical or different groups R^(b);    (C₃-C₈-cycloalkyl)-C₂-C₈-alkenyl; (C₃-C₈-cycloalkyl)-C₂-C₈-alkynyl;    tri(C₁-C₈)alkylsilyl; tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl;    aryl-C₁-C₈-alkyl which is optionally substituted by up to 6    identical or different groups R^(b); aryl-C₂-C₈-alkenyl which is    optionally substituted by up to 6 identical or different groups    R^(b); aryl-C₂-C₈-alkynyl which is optionally substituted by up to 6    identical or different groups R^(b); each of which is optionally    substituted; provided that R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ do not    represent hydrogen at the same time when R⁸ represents hydrogen or    trifluoromethyl.

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independently of one anotherparticularly preferably represent hydrogen, fluorine, chlorine, bromine,iodine; C₁-C₁₂-alkyl; C₁-C₆-haloalkyl having 1 to 9 identical ordifferent halogen atoms; C₃-C₆-cycloalkyl;(C₃-C₆-cycloalkyl)-C₁-C₆-alkyl; (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl;C₁-C₁₂-alkoxy; C₃-C₆-cycloalkyloxy; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyloxy;each of which is optionally substituted; provided that R¹, R², R³, R⁴,R⁵, R⁶ and R⁷ do not represent hydrogen at the same time when R⁸represents hydrogen or trifluoromethyl.

-   R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independently of one another very    particularly preferably represent hydrogen, methyl, ethyl, propyl,    isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, methoxy,    ethoxy, propyloxy, isopropyloxy, n-butyloxy, iso-butyloxy,    sec-butyloxy, tert-butyloxy; provided that R¹, R², R³, R⁴, R⁵, R⁶    and R⁷ do not represent hydrogen at the same time when R⁸ represents    hydrogen or trifluoromethyl.-   R¹ and R² can preferably form together with the carbon to which they    are attached an optionally substituted C₃-C₈-cycloalkyl; or may form    the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another    represent hydrogen, halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl having 1    to 9 identical or different halogen atoms or form together with the    carbon to which they are attached an optionally substituted    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₁₂-alkyl; C₁-C₆-haloalkyl    having 1 to 9 identical or different halogen atoms;    C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;    (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;    C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally    substituted by up to 6 identical or different groups R^(b); each of    which is optionally substituted).-   R¹ and R² can preferably form together with the carbon to which they    are attached an optionally substituted C₃-C₈-cycloalkyl; or may form    the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another    represent halogen C₁-C₁₂-alkyl, C₁-C₆-haloalkyl having 1 to 9    identical or different halogen atoms or form together with the    carbon to which they are attached an optionally substituted    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₁₂-alkyl; C₁-C₆-haloalkyl    having 1 to 9 identical or different halogen atoms;    C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;    (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;    C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally    substituted by up to 6 identical or different groups R^(b); each of    which is optionally substituted).-   R¹ and R² can particularly preferably form together with the carbon    to which they are attached an optionally substituted cyclopropyl,    cyclobutyl, cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y²    (where Y¹ and Y² independently of one another represent hydrogen,    fluorine, chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a    group ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl;    C₁-C₄-haloalkyl having 1 to 9 identical or different fluorine,    chlorine or bromine atoms; C₃-C₆-cycloalkyl;    (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl; C₂-C₆-alkenyl-C₁-C₈-alkyl;    C₂-C₆-alkynyl-C₁-C₈-alkyl; aryl-C₁-C₄-alkyl which is optionally    substituted by up to 5 identical or different groups R^(b); each of    which is optionally substituted).-   R¹ and R² can particularly preferably form together with the carbon    to which they are attached an optionally substituted cyclopropyl,    cyclobutyl, cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y²    (where Y¹ and Y² independently of one another represent fluorine,    chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl; C₁-C₄-haloalkyl    having 1 to 9 identical or different fluorine, chlorine or bromine    atoms; C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl;    C₂-C₆-alkenyl-C₁-C₈-alkyl; C₂-C₆-alkynyl-C₁-C₈-alkyl;    aryl-C₁-C₄-alkyl which is optionally substituted by up to 5    identical or different groups R^(b); each of which is optionally    substituted).-   R³ and R⁴ can preferably form together with the carbon to which they    are attached an optionally substituted C₃-C₈-cycloalkyl; or may form    the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another    represent hydrogen, halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl having 1    to 9 identical or different halogen atoms or form together with the    carbon to which they are attached an optionally substituted    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₁₂-alkyl; C₁-C₆-haloalkyl    having 1 to 9 identical or different halogen atoms;    C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;    (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;    C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally    substituted by up to 6 identical or different groups R^(b); each of    which is optionally substituted).-   R³ and R⁴ can preferably form together with the carbon to which they    are attached an optionally substituted C₃-C₈-cycloalkyl; or may form    the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another    represent halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl having 1 to 9    identical or different halogen atoms or form together with the    carbon to which they are attached an optionally substituted    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₁₂-alkyl; C₁-C₆-haloalkyl    having 1 to 9 identical or different halogen atoms;    C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;    (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;    C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally    substituted by up to 6 identical or different groups R^(b); each of    which is optionally substituted).-   R³ and R⁴ can particularly preferably form together with the carbon    to which they are attached an optionally substituted cyclopropyl,    cyclobutyl, cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y²    (where Y¹ and Y² independently of one another represent hydrogen,    fluorine, chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a    group ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl;    C₁-C₄-haloalkyl having 1 to 9 identical or different fluorine,    chlorine or bromine atoms; C₃-C₆-cycloalkyl;    (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl; C₂-C₆-alkenyl-C₁-C₈-alkyl;    C₂-C₆-alkynyl-C₁-C₈-alkyl; aryl-C₁-C₄-alkyl which is optionally    substituted by up to 5 identical or different groups R^(b); each of    which is optionally substituted).-   R³ and R⁴ can particularly preferably form together with the carbon    to which they are attached an optionally substituted cyclopropyl,    cyclobutyl, cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y²    (where Y¹ and Y² independently of one another represent fluorine,    chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl; C₁-C₄-haloalkyl    having 1 to 9 identical or different fluorine, chlorine or bromine    atoms; C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl;    C₂-C₆-alkenyl-C₁-C₈-alkyl; C₂-C₆-alkynyl-C₁-C₈-alkyl;    aryl-C₁-C₄-alkyl which is optionally substituted by up to 5    identical or different groups R^(b); each of which is optionally    substituted).-   R⁵ and R⁶ can preferably form together with the carbon to which they    are attached an optionally substituted C₃-C₈-cycloalkyl; or may form    the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another    represent halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl having 1 to 9    identical or different halogen atoms or form together with the    carbon to which they are attached an optionally substituted    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₁₂-alkyl; C₁-C₆-haloalkyl    having 1 to 9 identical or different halogen atoms;    C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;    (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;    C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally    substituted by up to 6 identical or different groups R^(b); each of    which is optionally substituted).-   R⁵ and R⁶ can particularly preferably form together with the carbon    to which they are attached an optionally substituted cyclopropyl,    cyclobutyl, cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y²    (where Y¹ and Y² independently of one another represent hydrogen,    fluorine, chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a    group ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl;    C₁-C₄-haloalkyl having 1 to 9 identical or different fluorine,    chlorine or bromine atoms; C₃-C₆-cycloalkyl;    (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl; C₂-C₆-alkenyl-C₁-C₈-alkyl;    C₂-C₆-alkynyl-C₁-C₈-alkyl; aryl-C₁-C₄-alkyl which is optionally    substituted by up to 5 identical or different groups R^(b); each of    which is optionally substituted).-   R⁵ and R⁶ can particularly preferably form together with the carbon    to which they are attached an optionally substituted cyclopropyl,    cyclobutyl, cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y²    (where Y¹ and Y² independently of one another represent fluorine,    chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl; C₁-C₄-haloalkyl    having 1 to 9 identical or different fluorine, chlorine or bromine    atoms; C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl;    C₂-C₆-alkenyl-C₁-C₈-alkyl; C₂-C₆-alkynyl-C₁-C₈-alkyl;    aryl-C₁-C₄-alkyl which is optionally substituted by up to 5    identical or different groups R^(b); each of which is optionally    substituted).-   R⁷ and R⁸ can preferably form together with the carbon to which they    are attached an optionally substituted C₃-C₈-cycloalkyl; or may form    the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another    represent hydrogen, halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl having 1    to 9 identical or different halogen atoms or form together with the    carbon to which they are attached an optionally substituted    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₁₂-alkyl; C₁-C₆-haloalkyl    having 1 to 9 identical or different halogen atoms;    C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;    (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;    C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally    substituted by up to 6 identical or different groups R^(b); each of    which is optionally substituted).-   R⁷ and R⁸ can preferably form together with the carbon to which they    are attached an optionally substituted C₃-C₈-cycloalkyl; or may form    the group ═C(Y¹)Y² (where Y¹ and Y² independently of one another    represent halogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl having 1 to 9    identical or different halogen atoms or form together with the    carbon to which they are attached an optionally substituted    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₁₂-alkyl; C₁-C₆-haloalkyl    having 1 to 9 identical or different halogen atoms;    C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₆-alkyl;    (C₃-C₆-cycloalkyl)-C₃-C₆-cycloalkyl; C₂-C₆-alkenyl-C₁-C₁₂-alkyl;    C₂-C₆-alkynyl-C₁-C₁₂-alkyl; aryl-C₁-C₆-alkyl which is optionally    substituted by up to 6 identical or different groups R^(b); each of    which is optionally substituted).-   R⁷ and R⁸ can particularly preferably form together with the carbon    to which they are attached an optionally substituted cyclopropyl,    cyclobutyl, cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y²    (where Y¹ and Y² independently of one another represent hydrogen,    fluorine, chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a    group ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl;    C₁-C₄-haloalkyl having 1 to 9 identical or different fluorine,    chlorine or bromine atoms; C₃-C₆-cycloalkyl;    (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl; C₂-C₆-alkenyl-C₁-C₈-alkyl;    C₂-C₆-alkynyl-C₁-C₈-alkyl; aryl-C₁-C₄-alkyl which is optionally    substituted by up to 5 identical or different groups R^(b); each of    which is optionally substituted).-   R⁷ and R⁸ can particularly preferably form together with the carbon    to which they are attached an optionally substituted cyclopropyl,    cyclobutyl, cyclopentyl, cyclohexyl; or may form the group ═C(Y¹)Y²    (where Y¹ and Y² independently of one another represent fluorine,    chlorine, bromine, methyl; ethyl, propyl, isopropyl) or a group    ═N—O—R^(c) (where R^(c) represents C₁-C₈-alkyl; C₁-C₄-haloalkyl    having 1 to 9 identical or different fluorine, chlorine or bromine    atoms; C₃-C₆-cycloalkyl; (C₃-C₆-cycloalkyl)-C₁-C₄-alkyl;    C₂-C₆-alkenyl-C₁-C₈-alkyl; C₂-C₆-alkynyl-C₁-C₈-alkyl;    aryl-C₁-C₄-alkyl which is optionally substituted by up to 5    identical or different groups R^(b); each of which is optionally    substituted).-   R¹ and R³ or R³ and R⁵ or R⁵ and R⁷ can preferably form together    with the carbons to which they are attached an optionally    substituted C₃-C₈-cycloalkyl.-   R¹ and R³ or R³ and R⁵ or R⁵ and R⁷ can particularly preferably form    together with the carbons to which they are attached an optionally    substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.-   R^(b) preferably represents halogen; nitro, cyano, C₁-C₈-alkyl;    C₁-C₄-haloalkyl having 1 to 9 identical or different halogen atoms;    C₁-C₆-alkoxy; C₁-C₄-haloalkoxy having 1 to 9 identical or different    halogen atoms; C₁-C₆-alkylsulfanyl; C₁-C₄-haloalkylsulfanyl having 1    to 9 identical or different halogen atoms; C₁-C₆-alkylsulfonyl;    C₁-C₄-haloalkylsulfonyl having 1 to 9 identical or different halogen    atoms; C₂-C₈-alkenyl; C₂-C₈-alkynyl; C₃-C₆-cycloalkyl; phenyl;    tri(C₁-C₆)alkylsilyl; tri(C₁-C₆)alkylsilyl-C₁-C₆-alkyl.-   R^(b) particularly preferably represents fluorine, chlorine,    bromine; C₁-C₆-alkyl; C₁-C₄-haloalkyl having 1 to 9 identical or    different halogen atoms; C₁-C₄-alkoxy; C₁-C₄-haloalkoxy having 1 to    9 identical or different halogen atoms; C₁-C₄-alkylsulfanyl;    C₁-C₄-haloalkylsulfanyl having 1 to 9 identical or different halogen    atoms; C₁-C₄-alkylsulfonyl; C₁-C₄-haloalkylsulfonyl having 1 to 9    identical or different halogen atoms; C₂-C₆-alkenyl; C₂-C₆-alkynyl;    C₃-C₆-cycloalkyl; phenyl; tri(C₁-C₄)alkylsilyl;    tri(C₁-C₄)alkylsilyl-C₁-C₄-alkyl.-   R^(b) very particularly preferably represents fluorine, chlorine,    bromine; methyl, ethyl, n-propyl, isopropyl, n-, s-, t-butyl,    trifluoromethyl, trichloromethyl, difluoromethyl, methoxy,    trifluoromethoxy, methylsulfanyl, trifluoromethylsulfanyl, vinyl,    allyl, ethinyl, propargyl, cyclopropyl, phenyl, trimethylsilyl.

Unless indicated otherwise, a group or a substituent which issubstituted according to the invention is substituted by one or moregroup selected in the list consisting of halogen; nitro, cyano,C₁-C₁₆-alkyl; C₁-C₆-haloalkyl having 1 to 9 identical or differenthalogen atoms; C₁-C₆-alkoxy; C₁-C₆-haloalkoxy having 1 to 9 identical ordifferent halogen atoms; C₁-C₆-alkylsulfanyl; C₁-C₆-haloalkylsulfanylhaving 1 to 9 identical or different halogen atoms; C₁-C₆-alkylsulfonyl;C₁-C₆-haloalkylsulfonyl having 1 to 9 identical or different halogenatoms; C₂-C₁₂-alkenyl; C₂-C₁₂-alkynyl; C₃-C₇-cycloalkyl; phenyl;tri(C₁-C₈)alkylsilyl; tri(C₁-C₈)alkylsilyl-C₁-C₈-alkyl.

Finally, it has been found that the novel (thio) carboxamides of theformula (I) have very good microbicidal properties and can be used forcontrolling unwanted microorganisms both in crop protection and in theprotection of materials.

The definition C₁-C₁₆-alkyl comprises the largest range defined here foran alkyl radical. Specifically, this definition comprises the meaningsmethyl, ethyl, n-, isopropyl, n-, iso-, sec-, tert-butyl, and also ineach case all isomeric pentyls, hexyls, heptyls, octyls, nonyls, decyls,undecyls, dodecyls, tridecyls, tetradecyls, pentadecyls, hexadecyls. Apreferred range is C₂-C₁₂-alkyl, such as ethyl and straight-chain orbranched propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl and dodecyl, particularly straight-chain or branchedC₃-C₁₀-alkyl, such as propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl,2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl,1-ethyl-3-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl,2-ethylpentyl, 1-propylbutyl, octyl, 1-methylheptyl, 2-methylheptyl,1-ethylhexyl, 2-ethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl,1-methyloctyl, 2-methyloctyl, 1-ethylheptyl, 2-ethylheptyl,1-propylhexyl, 2-propylhexyl, decyl, 1-methylnonyl, 2-methylnonyl,1-ethyloctyl, 2-ethyloctyl, 1-propylheptyl and 2-propylheptyl, inparticular propyl, 1-methylethyl, butyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1,1-dimethylethyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,pentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, 3-methylpentyl, heptyl,1-methylhexyl, 1-ethyl-3-methylbutyl, 1-methylheptyl, 1,2-dimethylhexyl,1,3-dimethyloctyl, 4-methyloctyl, 1,2,2,3-tetramethylbutyl,1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl, 1,3-dimethylpentyl,1,3-dimethylhexyl, 5-methyl-3-hexyl, 2-methyl-4-heptyl,2,6-dimethyl-4-heptyl and 1-methyl-2-cyclopropylethyl.

Halogen-substituted alkyl represents, for example, chloromethyl,dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl,chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl, pentafluoroethyl, 3-chloro-1-methylbutyl,2-chloro-1-methylbutyl, 1-chlorobutyl, 3,3-dichloro-1-methylbutyl,3-chloro-1-methylbutyl, 1-methyl-3-trifluoromethylbutyl,3-methyl-1-trifluoromethylbutyl.

The definition tri(C₁-C₈)alkylsilyl preferably represents the followingradicals: SiMe₃, SiMe₂Et, SiMe₂CHMe₂, SiMe₂CH₂CHMe₂, SiMe₂CH₂CMe₃,SiMe₂CMe₃, SiMe₂CH₂CH₂Me.

The definition C₂-C₁₆-alkenyl comprises the largest range defined herefor an alkenyl radical. Specifically, this definition comprises themeanings ethenyl, n-, isopropenyl, n-, iso-, sec-, tert-butenyl, andalso in each case all isomeric pentenyls, hexenyls, heptenyls, octenyls,nonenyls, decenyls, undecenyls, dodecenyls, tridecenyls, tetradecenyls,pentadecenyls, hexadecenyls, 1-methyl-1-propenyl, 1-ethyl-1-butenyl,2,4-dimethyl-1-pentenyl, 2,4-dimethyl-2-pentenyl.

The definition C₂-C₁₆-alkynyl comprises the largest range defined herefor an alkynyl radical. Specifically, this definition comprises themeanings ethynyl, n-, isopropynyl, n-, iso-, sec-, tert-butynyl, andalso in each case all isomeric pentynyls, hexynyls, heptynyls, octynyls,nonynyls, decynyls, undecynyls, dodecynyls, tridecynyls, tetradecynyls,pentadecynyls, hexadecynyls.

The definition cycloalkyl comprises monocyclic saturated hydrocarbylgroups having 3 to 8 carbon ring members, such as cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

The definition aryl comprises unsubstituted or substituted, aromatic,mono-, bi- or tricyclic ring, for example phenyl, naphthyl, anthracenyl(anthryl), phenanthracenyl (phenanthryl).

The definition heterocycle comprises unsubstituted or substituted,unsaturated heterocyclic 5- to 7-membered ring containing up to 4heteroatoms selected from N, O and S: for example 2-furyl, 3-furyl,2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrrolyl, 3-pyrazolyl,4-pyrazolyl, 5-pyrazolyl, 1-pyrazolyl, 1H-imidazol-2-yl,1H-imidazol-4-yl, 1H-imidazol-5-yl, 1H-imidazol-1-yl, 2-oxazolyl,4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl,3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,4-isothiazolyl, 5-isothiazolyl, 1H-1,2,3-triazol-1-yl,1H-1,2,3-triazol-4-yl, 1H-1,2,3-triazol-5-yl, 2H-1,2,3-triazol-2-yl,2H-1,2,3-triazol-4-yl, 1H-1,2,4-triazol-3-yl, 1H-1,2,4-triazol-5-yl,1H-1,2,4-triazol-1-yl, 4H-1,2,4-triazol-3-yl, 4H-1,2,4-triazol-4-yl,1H-tetrazol-1-yl, 1H-tetrazol-5-yl, 2H-tetrazol-2-yl, 2H-tetrazol-5-yl,1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,1,2,4-thiadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl,1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,3-thiadiazol-4-yl,1,2,3-thiadiazol-5-yl, 1,2,5-oxadiazol-3-yl, 1,2,5-thiadiazol-3-yl,2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl,1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl,1,2,4-triazin-6-yl.

Optionally substituted radicals may be mono- or polysubstituted, wherein the case of polysubstitution, the substituents may be identical ordifferent. Thus, the definition dialkylamino also embraces an aminogroup which is substituted asymmetrically by alkyl, such as, forexample, methylethylamino.

Halogen-substituted radicals, such as, for example, halogenoalkyl, aremono- or polyhalogenated. In the case of polyhalogenation, the halogenatoms may be identical or different. Here, halogen represents fluorine,chlorine, bromine and iodine, in particular fluorine, chlorine andbromine.

However, the general or preferred radical definitions or illustrationsgiven above can also be combined with one another as desired, i.e.including combinations between the respective ranges and preferredranges. They apply to the end products and, correspondingly, toprecursors and intermediates.

The radical definitions and explanations given above in general terms orstated within preferred ranges can, however, also be combined with oneanother as desired, i.e. including between the particular ranges andpreferred ranges. They apply both to the end products andcorrespondingly to precursors and intermediates. In addition, individualdefinitions may not apply.

Preference is given to those compounds of the formula (I) in which eachof the radicals have the above mentioned preferred definitions.

Particular preference is given to those compounds of the formula (I) inwhich each of the radicals have the above-mentioned particularlypreferred definitions.

Very particular preference is given to those compounds of the formula(I) in which each of the radicals have the above-mentioned veryparticularly preferred definitions.

In one embodiment of the invention within the compounds of formula (I)Hal¹ and Hal² each represent fluorine.

In one embodiment of the invention within the compounds of formula (I)Hal¹ represents fluorine and Hal² represents chlorine.

In one embodiment of the invention within the compounds of formula (I)R¹, R², R³, R⁴, R⁵ and R⁶ all represent hydrogen and R⁷ and R⁸ bothrepresent methyl.

In one embodiment of the invention within the compounds of formula (I)R², R³, R⁴, R⁵ and R⁶ all represent hydrogen and R¹, R⁷ and R⁸ allrepresent methyl.

If appropriate, the compounds according to the invention can be presentas mixtures of different possible isomeric forms, in particular ofstereoisomers, such as, for example, E and Z, threo and erythro, andalso optical isomers, and, if appropriate, also of tautomers. What isclaimed are both the E and the Z isomers, and also the threo anderythro, and the optical isomers, any mixtures of these isomers, and thepossible tautomeric forms.

If appropriate, the compounds of the present invention can exist in oneor more optical or chiral isomer forms depending on the number ofasymmetric centres in the compound. The invention thus relates equallyto all the optical isomers and to their racemic or scalemic mixtures(the term “scalemic” denotes a mixture of enantiomers in differentproportions) and to the mixtures of all the possible stereoisomers, inall proportions. The diastereoisomers and/or the optical isomers can beseparated according to the methods which are known per se by the manordinary skilled in the art.

If appropriate, the compounds of the present invention can also exist inone or more geometric isomer forms depending on the number of doublebonds in the compound. The invention thus relates equally to allgeometric isomers and to all possible mixtures, in all proportions. Thegeometric isomers can be separated according to general methods, whichare known per se by the man ordinary skilled in the art.

If appropriate, the compounds of the present invention can also exist inone or more geometric isomer forms depending on the relative position(syn/anti or cis/trans) of the substituents of ring B. The inventionthus relates equally to all syn/anti (or cis/trans) isomers and to allpossible syn/anti (or cis/trans) mixtures, in all proportions. Thesyn/anti (or cis/trans) isomers can be separated according to generalmethods, which are known per se by the man ordinary skilled in the art.

Illustration of the Processes and Intermediates

Carboxamides of the formula (I-a), i.e. carboxamides of formula (I)wherein T represents oxygen, are obtained when carbonyl halides or acidsof formula (II) are reacted with amines of formula (III-a) ifappropriate in the presence of a coupling agent, if appropriate in thepresence of an acid binder and if appropriate in the presence of adiluent [Process (a)]:

The formula (II) provides a general definition of the carbonyl halidesor acids required as starting materials for carrying out the Process (a)according to the invention.

In this formula (II) Hal¹ and Hal² have generally and preferably thosemeanings which have already been mentioned for these radicals inconnection with the description of the compounds of the formula (I). X³represents halogen, hydroxyl or an activated hydroxyl group, preferablyrepresents fluorine, chlorine or hydroxyl, particularly preferablychlorine or hydroxyl.

An activated hydroxyl group shall mean that the hydroxyl forms togetherwith the adjacent carbonyl an ester which spontaneously reacts with anamino group. Common activated esters include p-nitrophenyl,pentafluorophenyl and succinimido esters.

The carbonyl halides or acids of the formula (II) can be prepared fromcommercially available starting material using known procedures (cf. R.C. Larock Comprehensive organic transformations, 1989, VCH publishers).

The formula (III-a) provides a general definition of the amines requiredas starting materials for carrying out the Process (a) according to theinvention.

In this formula (III-a) Q, X, m, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ havegenerally, preferably, particularly preferably, very particularlypreferably those meanings which have already been mentioned for theseradicals in connection with the description of the compounds of theformula (I).

Thiocarboxamides of the formula (I-b), i.e. carboxamides of formula (I)wherein T represents sulfur, are obtained when carboxamides of theformula (I-a) are reacted with a thionating agent, optionally in thepresence of a diluent and if appropriate in the presence of a catalyticor stoichiometric or more quantity of a base [Process (b)]:

Compounds of formula (III-a) used as starting materials are prepared byknown methods (Fragrance chemistry: the science of the sense ofsmell/edited by Ernst T. Theimer—Synthetic Benzenoid Musks by T. W.Wood; Chemistry—A European Journal, 8(4), 853-858; 2002; Tetrahedron,59(37), 7389-7395; 2003; Journal of Medicinal Chemistry, 48(1), 71-90;2005; Bioorganic & Medicinal Chemistry Letters, 18(6), 1830-1834; 2008),are commercially available or can be prepared by reacting bromides offormula (III-b) with tert-butyl carbamates of formula (IV) in thepresence of a catalyst, optionally in the presence of an acid binder, inthe presence of a diluent followed by treatment with a suitable acid[Process (c)]:

The formula (III-b) provides a general definition of the bromidesrequired as starting materials for carrying out the Process (c)according to the invention.

In this formula (III-b) Q, X, m, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ havegenerally, preferably, particularly preferably, very particularlypreferably those meanings which have already been mentioned for theseradicals in connection with the description of the compounds of theformula (I).

In formula (IV) Q has generally, preferably, particularly preferably,very particularly preferably those meanings which have already beenmentioned for these radicals in connection with the description of thecompounds of the formula (I). Y represents hydrogen, C₁-C₆ alkyl, C₁-C₆alkyloxy, phenoxy, benzyloxy.

Compounds of formula (III-b) used as starting materials are prepared byknown methods (Fragrance chemistry: the science of the sense ofsmell/edited by Ernst T. Theimer—Synthetic Benzenoid Musks by T. W.Wood; Chemistry—A European Journal, 8(4), 853-858; 2002; Tetrahedron,59(37), 7389-7395; 2003; Journal of Medicinal Chemistry, 48(1), 71-90;2005; Bioorganic & Medicinal Chemistry Letters, 18(6), 1830-1834; 2008;U.S. Pat. No. 5,521,317, WO 2010/109301) or are commercially available.

The amines of the formula (III-a) are also obtained according to thefollowing schemes [Process (d)]:

In these formulas (V-a) and (V-b) Q, X, m, R¹, R², R³, R⁴, R⁵, R⁶, R⁷and R⁸ Compounds of formula (V-a) and (V-b) used as starting materialsare prepared by known methods.

Suitable diluents for carrying out the Processes (a), (b), (c), and (d)according to the invention are all inert organic solvents. Thesepreferably include aliphatic, alicyclic or aromatic hydrocarbons, suchas, for example, petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decaline; halogenatedhydrocarbons, such as, for example, chlorobenzene, dichlorobenzene,dichloromethane, chloroform, carbon tetrachloride, dichloroethane ortrichloroethane; ethers, such as diethyl ether, diisopropyl ether,methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran,1,2-dimethoxyethane, 1,2-diethoxyethane or anisol; ketones, such asacetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles,such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; their mixtures with water or pure water.

The Process (a) according to the invention is, if appropriate, carriedout in the presence of a suitable acid binder when X³ representshalogen. Suitable acid binders are all customary inorganic or organicbases. These preferably include alkaline earth metal or alkali metalhydrides, hydroxides, amides, alkoholates, acetates, carbonates orbicarbonates, such as, for example, sodium hydride, sodium amide,lithium diisopropylamide, sodium methoxide, sodium ethoxide, potassiumtert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate,sodium carbonate, potassium carbonate, potassium bicarbonate, sodiumbicarbonate or ammonium carbonate, and also tertiary amines, such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The Process (a) according to the invention is, if appropriate, carriedout in the presence of a suitable coupling agent when X³ representshydroxyl. Suitable coupling agents are all customary carbonylactivators. These preferably includeN-[3-(dimethylamino)propyl]-N′-ethyl-carbodiimide-hydrochloride,N,N′-di-sec-butylcarbodiimide, N,N′-dicyclohexylcarbodiimide,N,N′-diisopropylcarbodiimide,1-(3-(dimethylamino)propyl)-3-ethylcarbodiimide methiodide,2-bromo-3-ethyl-4-methylthiazolium tetrafluoroborate,N,N-bis[2-oxo-3-oxazolidinyl]-phosphorodiamidic chloride,chlorotripyrrolidinophosphonium hexafluorophosphate,bromtripyrrolidinophosphonium hexafluorophosphate,O-(1H-benzotriazol-1-yloxy)tris(dimethylamino)phosphoniumhexafluorophosphate,O-(1H-benzotriazol-1-yl)-N,N,N′,N′-tetramethyluroniumhexafluorophosphate,O-(1H-benzotriazol-1-yl)-N,N,N′,N′-bis(tetramethylene)uroniumhexafluorophosphate,O-(1H-benzotriazol-1-yl)-N,N,N′,N′-bis(tetramethylene)uroniumtetrafluoroborate, N,N,N′,N′-bis(tetramethylene)chlorouroniumtetrafluoroborate, O-(7-azabenzotriazol-1-yl)-N,N,N,N-tetramethyluroniumhexafluorophosphate and 1-hydroxybenzotriazole. These reagents can beemployed separately, but also in combination.

When carrying out the Process (a) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures of from 0° C. to150° C., preferably at temperatures of from 20° C. to 110° C.

For carrying out the Process (a) according to the invention forpreparing the compounds of the formula (I-a) in general from 0.2 to 5mol, preferably from 0.5 to 2 mol, of amine of the formula (III-a) areemployed per mole of the carbonyl halide or acid of the formula (II).Work-up is carried out by customary methods.

For carrying out the Process (b) according to the invention forpreparing the compounds of the formula (I-b) starting amide derivativesof formula (I-a) can be prepared according to Process (a).

Suitable thionating agents for carrying out Process (b) according to theinvention can be sulfur (S), sulfhydric acid (H₂S), sodium sulfide(Na₂S), sodium hydrosulfide (NaHS), boron trisulfide (B₂S₃),bis(diethylaluminium) sulfide ((AlEt₂)₂S), ammonium sulfide ((NH₄)₂S),phosphorous pentasulfide (P₂S₅), Lawesson's reagent(2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide) ora polymer-supported thionating reagent such as described in J. Chem.Soc., Perkin 1 2001, 358.

Process (c) is performed in the presence of a catalyst, optionally inthe presence of an acid binder, optionally in the presence of a diluentand followed by treatment with a suitable acid.

Suitable acids for this purpose are chosen amongst usual Brønsted acidssuch as for example HCl, H₂SO₄, KHSO₄, AcOH, trifluoroacetic acid,p-toluenesulfonic acid, camphorsulfonic acid, triethanolamine-HCl,Pyridine HCl.

Suitable catalysts for carrying out processes (c) and (d) according tothe invention may be chosen from metal salt or complex. Suitable metalderivatives for this purpose are based on palladium or copper. Suitablemetal salts or complexes for this purpose are palladium chloride,palladium acetate, tetrakis(triphenylphosphine)palladium,bis(triphenylphosphine)palladium dichloride or1,1′-bis(diphenylphosphino) ferrocenepalladium(II) chloride, copperiodide, copper bromide, copper thiophene carboxylate, coppertrifluoromethane sulfonate, copper (I) oxide

It is also possible to generate a palladium complex in the reactionmixture by separate addition to the reaction of a palladium salt and aligand or salt, such as a phosphine, for example triethylphosphine,tri-tert-butylphosphine, tricyclohexylphosphine,2-(dicyclohexylphosphine)biphenyl, 2-(di-tert-butylphosphin)biphenyl,2-(dicyclohexylphosphine)-2′-(N,N-dimethylamino)-biphenyl,triphenylphosphine, tris-(o-tolyl)phosphine, sodium3-(diphenylphosphino)benzolsulfonate, tris-2-(methoxyphenyl)phosphine,2,2′-bis-(diphenylphosphine)-1,1′-binaphthyl,1,4-bis-(diphenylphosphine)butane, 1,2-bis-(diphenylphosphine)ethane,1,4-bis-(dicyclohexylphosphine)butane,1,2-bis-(dicyclohexylphosphine)ethane,2-(dicyclohexylphosphine)-2′-(N,N-dimethylamino)biphenyl,bis(diphenylphosphino)ferrocene, tris-(2,4-tert-butylphenyl)-phosphite,(R)-(−)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi-tert-butylphosphine,(S)-(+)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine,(R)-(−)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine,(5)(+)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylphosphineor 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride.

It is also possible to generate a copper complex in the reaction mixtureby separate addition to the reaction of a copper salt and a ligand orsalt, such as a diamine for example cyclohexyl 1,2-diamine,N,N′-dimethylethylene diamine, cyclohexyl N,N′-dimethylamine.

It is also advantageous to choose the appropriate catalyst and/or ligandfrom commercial catalogues such as “Metal Catalysts for OrganicSynthesis” by Strem Chemicals or “Phosphorous Ligands and Compounds” byStrem Chemicals.

When carrying out the Process (c) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures of from 0° C. to150° C., preferably at temperatures of from 20° C. to 110° C.

For carrying out the Process (c) according to the invention forpreparing the compounds of the formula (III-a) in general from 0.2 to 5mol, preferably from 0.5 to 2 mol, of compound of the formula (IV) areemployed per mole of bromides of the formula (III-b). Work-up is carriedout by customary methods.

When carrying out The Process (d) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures of from 0° C. to150° C., preferably at temperatures of from 60° C. to 140° C.

For carrying out the Process (d) according to the invention forpreparing the compounds of the formula (I-a) in general from 0.2 to 5mol, preferably from 0.5 to 2 mol, of compound of the formula (V) areemployed per mole of the bromides of the formula (III-b). Work-up iscarried out by customary methods.

Suitable bases for carrying out the processes (b) according to theinvention can be inorganic and organic bases which are customary forsuch reactions. Preference is given to using alkaline earth metal,alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides,such as sodium hydroxide, sodium hydride, calcium hydroxide, potassiumhydroxide, potassium tert-butoxide or other ammonium hydroxide, alkalimetal carbonates, such as sodium carbonate, potassium carbonate,potassium bicarbonate, sodium bicarbonate, cesium carbonate, alkalimetal or alkaline earth metal acetates, such as sodium acetate,potassium acetate, calcium acetate, and also tertiary amines, such astrimethylamine, triethylamine, diisopropylethylamine, tributylamine,N,N-dimethylaniline, pyridine, N-methylpiperidine,N,N-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO),1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

Suitable acid binders for carrying out the processes (a), (c), and (d)according to the invention can be inorganic and organic bases which arecustomary for such reactions. Preference is given to using alkalineearth metal, alkali metal hydride, alkali metal hydroxides or alkalimetal alkoxides, such as sodium hydroxide, sodium hydride, calciumhydroxide, potassium hydroxide, potassium tert-butoxide or otherammonium hydroxide, alkali metal carbonates, such as sodium carbonate,potassium carbonate, potassium bicarbonate, sodium bicarbonate, cesiumcarbonate, alkali metal or alkaline earth metal acetates, such as sodiumacetate, potassium acetate, calcium acetate, and also tertiary amines,such as trimethylamine, triethylamine, diisopropylethylamine,tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine,N,N-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO),1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

The present invention also describes novel intermediates being compoundsaccording to formula (III-a)

wherein

-   -   Q represents hydrogen;    -   X represents fluorine;    -   m represents 0 or 1;    -   R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independently from each other        represent hydrogen or methyl;    -   R⁷ and R⁸ form the group ═C(Y¹)Y² (where Y¹ and Y² independently        of one another represent hydrogen or a group ═N—O—R^(c) (where        R^(c) represents methyl or ethyl).

The Processes (a), (b), (c) and (d) are generally carried out underatmospheric pressure. However, it is also possible to operate underelevated or reduced pressure—in general between 0.1 bar and 10 bar.

Composition/Formulation

The present invention further relates to a crop protection compositionfor controlling unwanted microorganisms, especially unwanted fungi andbacteria, comprising an effective and non-phytotoxic amount of theinventive active ingredients. These are preferably fungicidalcompositions which comprise agriculturally suitable auxiliaries,solvents, carriers, surfactants or extenders.

In the context of the present invention, “control of harmfulmicroorganisms” means a reduction in infestation by harmfulmicroorganisms, compared with the untreated plant measured as fungicidalefficacy, preferably a reduction by 25-50%, compared with the untreatedplant (100%), more preferably a reduction by 40-79%, compared with theuntreated plant (100%); even more preferably, the infection by harmfulmicroorganisms is entirely suppressed (by 70-100%). The control may becurative, i.e. for treatment of already infected plants, or protective,for protection of plants which have not yet been infected.

An “effective but non-phytotoxic amount” means an amount of theinventive composition which is sufficient to control the fungal diseaseof the plant in a satisfactory manner or to eradicate the fungal diseasecompletely, and which, at the same time, does not cause any significantsymptoms of phytotoxicity. In general, this application rate may varywithin a relatively wide range. It depends on several factors, forexample on the fungus to be controlled, the plant, the climaticconditions and the ingredients of the inventive compositions.

Suitable organic solvents include all polar and non-polar organicsolvents usually employed for formulation purposes. Preferable thesolvents are selected from ketones, e.g. methyl-isobutyl-ketone andcyclohexanone, amides, e.g. dimethyl formamide and alkanecarboxylic acidamides, e.g. N,N-dimethyl decaneamide and N,N-dimethyl octanamide,furthermore cyclic solvents, e.g. N-methyl-pyrrolidone,N-octyl-pyrrolidone, N-dodecylpyrrolidone, N-octyl-caprolactame,N-dodecyl-caprolactame and butyrolactone, furthermore strong polarsolvents, e.g. dimethylsulfoxide, and aromatic hydrocarbons, e.g. xylol,Solvesso™, mineral oils, e.g. white spirit, petroleum, alkyl benzenesand spindle oil, also esters, e.g. propyleneglycol-monomethyletheracetate, adipic acid dibutylester, acetic acid hexylester, acetic acidheptylester, citric acid tri-n-butylester and phthalic aciddi-n-butylester, and also alkohols, e.g. benzyl alcohol and1-methoxy-2-propanol.

According to the invention, a carrier is a natural or synthetic, organicor inorganic substance with which the active ingredients are mixed orcombined for better applicability, in particular for application toplants or plant parts or seed. The carrier, which may be solid orliquid, is generally inert and should be suitable for use inagriculture.

Useful solid or liquid carriers include: for example ammonium salts andnatural rock dusts, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and synthetic rockdusts, such as finely divided silica, alumina and natural or syntheticsilicates, resins, waxes, solid fertilizers, water, alcohols, especiallybutanol, organic solvents, mineral and vegetable oils, and derivativesthereof. Mixtures of such carriers can likewise be used.

Suitable solid filler and carrier include inorganic particles, e.g.carbonates, silikates, sulphates and oxides with an average particlesize of between 0.005 and 20 μm, preferably of between 0.02 to 10 μm,for example ammonium sulphate, ammonium phosphate, urea, calciumcarbonate, calcium sulphate, magnesium sulphate, magnesium oxide,aluminium oxide, silicium dioxide, so-called fine-particle silica,silica gels, natural or synthetic silicates, and alumosilicates andplant products like cereal flour, wood powder/sawdust and cellulosepowder.

Useful solid carriers for granules include: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepiolite,dolomite, and synthetic granules of inorganic and organic meals, andalso granules of organic material such as sawdust, coconut shells, maizecobs and tobacco stalks.

Useful liquefied gaseous extenders or carriers are those liquids whichare gaseous at standard temperature and under standard pressure, forexample aerosol propellants such as halohydrocarbons, and also butane,propane, nitrogen and carbon dioxide.

In the formulations, it is possible to use tackifiers such ascarboxymethylcellulose, and natural and synthetic to polymers in theform of powders, granules or latices, such as gum arabic, polyvinylalcohol and polyvinyl acetate, or else natural phospholipids, such ascephalins and lecithins, and synthetic phospholipids. Further additivesmay be mineral and vegetable oils.

If the extender used is water, it is also possible to employ, forexample, organic solvents as auxiliary solvents.

Useful liquid solvents are essentially: aromatics such as xylene,toluene or alkylnaphthalenes, chlorinated aromatics and chlorinatedaliphatic hydrocarbons such as chlorobenzenes, chloroethylenes ordichloromethane, aliphatic hydrocarbons such as cyclohexane orparaffins, for example mineral oil fractions, mineral and vegetableoils, alcohols such as butanol or glycol and their ethers and esters,ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents such as dimethylformamide anddimethyl sulphoxide, and also water.

Suitable surfactants (adjuvants, emulsifiers, dispersants, protectivecolloids, wetting agent and adhesive) include all common ionic andnon-ionic substances, for example ethoxylated nonylphenols, polyalkyleneglycolether of linear or branched alcohols, reaction products of alkylphenols with ethylene oxide and/or propylene oxide, reaction products offatty acid amines with ethylene oxide and/or propylene oxide,furthermore fattic acid esters, alkyl sulfonates, alkyl sulphates, alkylethersulphates, alkyl etherphosphates, arylsulphate, ethoxylatedarylalkylphenols, e.g. tristyryl-phenol-ethoxylates, furthermoreethoxylated and propoxylated arylalkylphenols like sulphated orphosphated arylalkylphenol-ethoxylates and -ethoxy- and -propoxylates.Further examples are natural and synthetic, water soluble polymers, e.g.lignosulphonates, gelatine, gum arabic, phospholipides, starch,hydrophobic modified starch and cellulose derivatives, in particularcellulose ester and cellulose ether, further polyvinyl alcohol,polyvinyl acetate, polyvinyl pyrrolidone, polyacrylic acid,polymethacrylic acid and co-polymerisates of (meth)acrylic acid and(meth)acrylic acid esters, and further co-polymerisates of methacrylicacid and methacrylic acid esters which are neutralized with alkalimetalhydroxide and also condensation products of optionally substitutednaphthalene sulfonic acid salts with formaldehyde. The presence of asurfactant is necessary if one of the active ingredients and/or one ofthe inert carriers is insoluble in water and when application iseffected in water. The proportion of surfactants is between 5 and 40percent by weight of the inventive composition.

It is possible to use dyes such as inorganic pigments, for example ironoxide, titanium oxide and Prussian Blue, and organic dyes such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

Antifoams which may be present in the formulations include e.g. siliconeemulsions, longchain alcohols, fatty acids and their salts as well asfluoroorganic substances and mixtures thereof.

Examples of thickeners are polysaccharides, e.g. xanthan gum or veegum,silicates, e.g. attapulgite, bentonite as well as fine-particle silica.

If appropriate, it is also possible for other additional components tobe present, for example protective colloids, binders, adhesives,thickeners, thixotropic substances, penetrants, stabilizers,sequestrants, complexing agents. In general, the active ingredients canbe combined with any solid or liquid additive commonly used forformulation purposes.

The inventive active ingredients or compositions can be used as such or,depending on their particular physical and/or chemical properties, inthe form of their formulations or the use forms prepared therefrom, suchas aerosols, capsule suspensions, cold-fogging concentrates,warm-fogging concentrates, encapsulated granules, fine granules,flowable concentrates for the treatment of seed, ready-to-use solutions,dustable powders, emulsifiable concentrates, oil-in-water emulsions,water-in-oil emulsions, macrogranules, microgranules, oil-dispersiblepowders, oil-miscible flowable concentrates, oil-miscible liquids, gas(under pressure), gas generating product, foams, pastes, pesticidecoated seed, suspension concentrates, suspoemulsion concentrates,soluble concentrates, suspensions, wettable powders, soluble powders,dusts and granules, water-soluble and water-dispersible granules ortablets, water-soluble and water-dispersible powders for the treatmentof seed, wettable powders, natural products and synthetic substancesimpregnated with active ingredient, and also microencapsulations inpolymeric substances and in coating materials for seed, and also ULVcold-fogging and warm-fogging formulations.

The inventive compositions include not only formulations which arealready ready for use and can be applied with a suitable apparatus tothe plant or the seed, but also commercial concentrates which have to bediluted with water prior to use. Customary applications are for exampledilution in water and subsequent spraying of the resulting spray liquor,application after dilution in oil, direct application without dilution,seed treatment or soil application of granules.

The inventive compositions and formulations generally contain between0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1and 95% by weight, more preferably between 0.5 and 90% of activeingredient, most preferably between 10 and 70% by weight. For specialapplications, e.g. for protection of wood and derived timber productsthe inventive compositions and formulations generally contain between0.0001 and 95% by weight, preferably 0.001 to 60% by weight of activeingredient.

The contents of active ingredient in the application forms prepared fromthe commercial formulations may vary in a broad range. The concentrationof the active ingredients in the application forms is generally between0.000001 to 95% by weight, preferably between 0.0001 and 2% by weight.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active ingredients with at least one customaryextender, solvent or diluent, adjuvant, emulsifier, dispersant, and/orbinder or fixative, wetting agent, water repellent, if appropriatedesiccants and UV stabilizers and, if appropriate, dyes and pigments,antifoams, preservatives, inorganic and organic thickeners, adhesives,gibberellins and also further processing auxiliaries and also water.Depending on the formulation type to be prepared further processingsteps are necessary, e.g. wet grinding, dry grinding and granulation.

The inventive active ingredients may be present as such or in their(commercial) formulations and in the use forms prepared from theseformulations as a mixture with other (known) active ingredients, such asinsecticides, attractants, sterilants, bactericides, acaricides,nematicides, fungicides, growth regulators, herbicides, fertilizers,safeners and/or semiochemicals.

The inventive treatment of the plants and plant parts with the activeingredients or compositions is effected directly or by action on theirsurroundings, habitat or storage space by the customary treatmentmethods, for example by dipping, spraying, atomizing, irrigating,evaporating, dusting, fogging, broadcasting, foaming, painting,spreading-on, watering (drenching), drip irrigating and, in the case ofpropagation material, especially in the case of seeds, also by dry seedtreatment, wet seed treatment, slurry treatment, incrustation, coatingwith one or more coats, etc. It is also possible to deploy the activeingredients by the ultra-low volume method or to inject the activeingredient preparation or the active ingredient itself into the soil.

Plant/Crop Protection

The inventive active ingredients or compositions have potentmicrobicidal activity and can be used for control of unwantedmicroorganisms, such as fungi and bacteria, in crop protection and inthe protection of materials.

The invention also relates to a method for controlling unwantedmicroorganisms, characterized in that the inventive active ingredientsare applied to the phytopathogenic fungi, phytopathogenic bacteriaand/or their habitat.

Fungicides can be used in crop protection for control of phytopathogenicfungi. They are characterized by an outstanding efficacy against a broadspectrum of phytopathogenic fungi, including soilborne pathogens, whichare in particular members of the classes Plasmodiophoromycetes,Peronosporomycetes (Syn. Oomycetes), Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes (Syn. Fungi imperfecti).Some fungicides are systemically active and ca be used in plantprotection as foliar, seed dressing or soil fungicide. Furthermore, theyare suitable for combating fungi, which inter alia infest wood or rootsof plant.

Bactericides can be used in crop protection for control ofPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Non-limiting examples of pathogens of fungal diseases which can betreated in accordance with the invention include:

diseases caused by powdery mildew pathogens, for example Blumeriaspecies, for example Blumeria graminis; Podosphaera species, for examplePodosphaera leucotricha; Sphaerotheca species, for example Sphaerothecafuliginea; Uncinula species, for example Uncinula necator;diseases caused by rust disease pathogens, for example Gymnosporangiumspecies, for example Gymnosporangium sabinae; Hemileia species, forexample Hemileia vastatrix; Phakopsora species, for example Phakopsorapachyrhizi and Phakopsora meibomiae; Puccinia species, for examplePuccinia recondite, P. triticina, P. graminis or P. striiformis;Uromyces species, for example Uromyces appendiculatus;diseases caused by pathogens from the group of the Oomycetes, forexample Albugo species, for example Algubo candida; Bremia species, forexample Bremia lactucae; Peronospora species, for example Peronosporapisi or P. brassicae; Phytophthora species, for example Phytophthorainfestans; Plasmopara species, for example Plasmopara viticola;Pseudoperonospora species, for example Pseudoperonospora humuli orPseudoperonospora cubensis; Pythium species, for example Pythiumultimum;leaf blotch diseases and leaf wilt diseases caused, for example, byAlternaria species, for example Alternaria solani; Cercospora species,for example Cercospora beticola; Cladiosporium species, for exampleCladiosporium cucumerinum; Cochliobolus species, for exampleCochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium),Cochliobolus miyabeanus; Colletotrichum species, for exampleColletotrichum lindemuthanium; Cycloconium species, for exampleCycloconium oleaginum; Diaporthe species, for example Diaporthe citri;Elsinoe species, for example Elsinoe fawcettii; Gloeosporium species,for example Gloeosporium laeticolor; Glomerella species, for exampleGlomerella cingulata; Guignardia species, for example Guignardiabidwelli; Leptosphaeria species, for example Leptosphaeria maculans,Leptosphaeria nodorum; Magnaporthe species, for example Magnaporthegrisea; Microdochium species, for example Microdochium nivale;Mycosphaerella species, for example Mycosphaerella graminicola, M.arachidicola and M. fijiensis; Phaeosphaeria species, for examplePhaeosphaeria nodorum; Pyrenophora species, for example Pyrenophorateres, Pyrenophora tritici repentis; Ramularia species, for exampleRamularia collo-cygni, Ramularia areola; Rhynchosporium species, forexample Rhynchosporium secalis; Septoria species, for example Septoriaapii, Septoria lycopersii; Typhula species, for example Typhulaincarnate; Venturia species, for example Venturia inaequalis;root and stem diseases caused, for example, by Corticium species, forexample Corticium graminearum; Fusarium species, for example Fusariumoxysporum; Gaeumannomyces species, for example Gaeumannomyces graminis;Rhizoctonia species, such as, for example Rhizoctonia solani;Sarocladium diseases caused for example by Sarocladium oryzae;Sclerotium diseases caused for example by Sclerotium oryzae; Tapesiaspecies, for example Tapesia acuformis; Thielaviopsis species, forexample Thielaviopsis basicola;ear and panicle diseases (including corn cobs) caused, for example, byAlternaria species, for example Alternaria spp.; Aspergillus species,for example Aspergillus flavus; Cladosporium species, for exampleCladosporium cladosporioides; Claviceps species, for example Clavicepspurpurea; Fusarium species, for example Fusarium culmorum; Gibberellaspecies, for example Gibberella zeae; Monographella species, for exampleMonographella nivalis; Septoria species, for example Septoria nodorum;diseases caused by smut fungi, for example Sphacelotheca species, forexample Sphacelotheca reiliana; Tilletia species, for example Tilletiacaries, T. controversa; Urocystis species, for example Urocystisocculta; Ustilago species, for example Ustilago nuda, U. nuda tritici;fruit rot caused, for example, by Aspergillus species, for exampleAspergillus flavus; Botrytis species, for example Botrytis cinerea;Penicillium species, for example Penicillium expansum and P.purpurogenum; Sclerotinia species, for example Sclerotinia sclerotiorum;Verticilium species, for example Verticilium alboatrum;seed and soilborne decay, mould, wilt, rot and damping-off diseasescaused, for example, by Alternaria species, caused for example byAlternaria brassicicola; Aphanomyces species, caused for example byAphanomyces euteiches; Ascochyta species, caused for example byAscochyta lentis; Aspergillus species, caused for example by Aspergillusflavus; Cladosporium species, caused for example by Cladosporiumherbarum; Cochliobolus species, caused for example by Cochliobolussativus; (Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium);Colletotrichum species, caused for example by Colletotrichum coccodes;Fusarium species, caused for example by Fusarium culmorum; Gibberellaspecies, caused for example by Gibberella zeae; Macrophomina species,caused for example by Macrophomina phaseolina; Monographella species,caused for example by Monographella nivalis; Penicillium species, causedfor example by Penicillium expansum; Phoma species, caused for exampleby Phoma lingam; Phomopsis species, caused for example by Phomopsissojae; Phytophthora species, caused for example by Phytophthoracactorum; Pyrenophora species, caused for example by Pyrenophoragraminea; Pyricularia species, caused for example by Pyricularia oryzae;Pythium species, caused for example by Pythium ultimum; Rhizoctoniaspecies, caused for example by Rhizoctonia solani; Rhizopus species,caused for example by Rhizopus oryzae; Sclerotium species, caused forexample by Sclerotium rolfsii; Septoria species, caused for example bySeptoria nodorum; Typhula species, caused for example by Typhulaincarnate; Verticillium species, caused for example by Verticilliumdahliae;cancers, galls and witches' broom caused, for example, by Nectriaspecies, for example Nectria galligena; wilt diseases caused, forexample, by Monilinia species, for example Monilinia laxa;leaf blister or leaf curl diseases caused, for example, by Exobasidiumspecies, for example Exobasidium vexans; Taphrina species, for exampleTaphrina deformans;decline diseases of wooden plants caused, for example, by Esca disease,caused for example by Phaemoniella clamydospora, Phaeoacremoniumaleophilum and Fomitiporia mediterranea; Eutypa dyeback, caused forexample by Eutypa lata; Ganoderma diseases caused for example byGanoderma boninense; Rigidoporus diseases caused for example byRigidoporus lignosus;diseases of flowers and seeds caused, for example, by Botrytis species,for example Botrytis cinerea; diseases of plant tubers caused, forexample, by Rhizoctonia species, for example Rhizoctonia solani;Helminthosporium species, for example Helminthosporium solani;Club root caused, for example, by Plasmodiophora species, for examplePlamodiophora brassicae;diseases caused by bacterial pathogens, for example Xanthomonas species,for example Xanthomonas campestris pv. oryzae; Pseudomonas species, forexample Pseudomonas syringae pv. lachrymans; Erwinia species, forexample Erwinia amylovora.

The following diseases of soya beans can be controlled with preference:

Fungal diseases on leaves, stems, pods and seeds caused, for example, byAlternaria leaf spot (Alternaria spec. atrans tenuissima), Anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphacelomaglycines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola).Fungal diseases on roots and the stem base caused, for example, by blackroot rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthephaseolorum), stem canker (Diaporthe phaseolorum var. caulivora),phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophoragregata), pythium rot (Pythium aphanidermatum, Pythium irregulare,Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctoniaroot rot, stem decay, and damping-off (Rhizoctonia solani), sclerotiniastem decay (Sclerotinia sclerotiorum), sclerotinia southern blight(Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

The inventive fungicidal compositions can be used for curative orprotective/preventive control of phytopathogenic fungi. The inventiontherefore also relates to curative and protective methods forcontrolling phytopathogenic fungi by the use of the inventive activeingredients or compositions, which are applied to the seed, the plant orplant parts, the fruit or the soil in which the plants grow.

The fact that the active ingredients are well tolerated by plants at theconcentrations required for controlling plant diseases allows thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

According to the invention all plants and plant parts can be treated. Byplants is meant all plants and plant populations such as desirable andundesirable wild plants, cultivars and plant varieties (whether or notprotectable by plant variety or plant breeder's rights). Cultivars andplant varieties can be plants obtained by conventional propagation andbreeding methods which can be assisted or supplemented by one or morebiotechnological methods such as by use of double haploids, protoplastfusion, random and directed mutagenesis, molecular or genetic markers orby bioengineering and genetic engineering methods. By plant parts ismeant all above ground and below ground parts and organs of plants suchas shoot, leaf, blossom and root, whereby for example leaves, needles,stems, branches, blossoms, fruiting bodies, fruits and seed as well asroots, corms and rhizomes are listed. Crops and vegetative andgenerative propagating material, for example cuttings, corms, rhizomes,runners and seeds also belong to plant parts.

The inventive active ingredients, when they are well tolerated byplants, have favourable homeotherm toxicity and are well tolerated bythe environment, are suitable for protecting plants and plant organs,for enhancing harvest yields, for improving the quality of the harvestedmaterial. They can preferably be used as crop protection compositions.They are active against normally sensitive and resistant species andagainst all or some stages of development.

Plants which can be treated in accordance with the invention include thefollowing main crop plants: maize, soya bean, alfalfa, cotton,sunflower, Brassica oil seeds such as Brassica napus (e.g. canola,rapeseed), Brassica rapa, B. juncea (e.g. (field) mustard) and Brassicacarinata, Arecaceae sp. (e.g. oilpalm, coconut), rice, wheat, sugarbeet, sugar cane, oats, rye, barley, millet and sorghum, triticale,flax, nuts, grapes and vine and various fruit and vegetables fromvarious botanic taxa, e.g. Rosaceae sp. (e.g. pome fruits such as applesand pears, but also stone fruits such as apricots, cherries, almonds,plums and peaches, and berry fruits such as strawberries, raspberries,red and black currant and gooseberry), Ribesioidae sp., Juglandaceaesp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp.,Oleaceae sp. (e.g. olive tree), Actinidaceae sp., Lauraceae sp. (e.g.avocado, cinnamon, camphor), Musaceae sp. (e.g. banana trees andplantations), Rubiaceae sp. (e.g. coffee), Theaceae sp. (e.g. tea),Sterculiceae sp., Rutaceae sp. (e.g. lemons, oranges, mandarins andgrapefruit); Solanaceae sp. (e.g. tomatoes, potatoes, peppers, capsicum,aubergines, tobacco), Liliaceae sp., Compositae sp. (e.g. lettuce,artichokes and chicory—including root chicory, endive or commonchicory), Umbelliferae sp. (e.g. carrots, parsley, celery and celeriac),Cucurbitaceae sp. (e.g. cucumbers—including gherkins, pumpkins,watermelons, calabashes and melons), Alliaceae sp. (e.g. leeks andonions), Cruciferae sp. (e.g. white cabbage, red cabbage, broccoli,cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes,horseradish, cress and chinese cabbage), Leguminosae sp. (e.g. peanuts,peas, lentils and beans—e.g. common beans and broad beans),Chenopodiaceae sp. (e.g. Swiss chard, fodder beet, spinach, beetroot),Linaceae sp. (e.g. hemp), Cannabeacea sp. (e.g. cannabis), Malvaceae sp.(e.g. okra, cocoa), Papaveraceae (e.g. poppy), Asparagaceae (e.g.asparagus); useful plants and ornamental plants in the garden and woodsincluding turf, lawn, grass and Stevia rebaudiana; and in each casegenetically modified types of these plants.

Resistance Induction/Plant Health and Other Effects

The active compounds according to the invention also exhibit a potentstrengthening effect in plants. Accordingly, they can be used formobilizing the defences of the plant against attack by undesirablemicroorganisms.

Plant-strengthening (resistance-inducing) substances are to beunderstood as meaning, in the present context, those substances whichare capable of stimulating the defence system of plants in such a waythat the treated plants, when subsequently inoculated with undesirablemicroorganisms, develop a high degree of resistance to thesemicroorganisms.

The active compounds according to the invention are also suitable forincreasing the yield of crops. In addition, they show reduced toxicityand are well tolerated by plants.

Further, in context with the present invention plant physiology effectscomprise the following:

Abiotic stress tolerance, comprising temperature tolerance, droughttolerance and recovery after drought stress, water use efficiency(correlating to reduced water consumption), flood tolerance, ozonestress and UV tolerance, tolerance towards chemicals like heavy metals,salts, pesticides (safener) etc.Biotic stress tolerance, comprising increased fungal resistance andincreased resistance against nematodes, viruses and bacteria. In contextwith the present invention, biotic stress tolerance preferably comprisesincreased fungal resistance and increased resistance against nematodesIncreased plant vigor, comprising plant health/plant quality and seedvigor, reduced stand failure, improved appearance, increased recovery,improved greening effect and improved photosynthetic efficiency.Effects on Plant Hormones and/or Functional Enzymes.

Effects on growth regulators (promoters), comprising earliergermination, better emergence, more developed root system and/orimproved root growth, increased ability of tillering, more productivetillers, earlier flowering, increased plant height and/or biomass,shorting of stems, improvements in shoot growth, number of kernels/ear,number of ears/m², number of stolons and/or number of flowers, enhancedharvest index, bigger leaves, less dead basal leaves, improvedphyllotaxy, earlier maturation/earlier fruit finish, homogenous riping,increased duration of grain filling, better fruit finish, biggerfruit/vegetable size, sprouting resistance and reduced lodging.

Increased yield, referring to total biomass per hectare, yield perhectare, kernel/fruit weight, seed size and/or hectolitre weight as wellas to increased product quality, comprising:

improved processability relating to size distribution (kernel, fruit,etc.), homogenous riping, grain moisture, better milling, bettervinification, better brewing, increased juice yield, harvestability,digestibility, sedimentation value, falling number, pod stability,storage stability, improved fiber length/strength/uniformity, increaseof milk and/or meet quality of silage fed animals, adaption to cookingand frying;further comprising improved marketability relating to improvedfruit/grain quality, size distribution (kernel, fruit, etc.), increasedstorage/shelf-life, firmness/softness, taste (aroma, texture, etc.),grade (size, shape, number of berries, etc.), number of berries/fruitsper bunch, crispness, freshness, coverage with wax, frequency ofphysiological disorders, colour, etc.;further comprising increased desired ingredients such as e.g. proteincontent, fatty acids, oil content, oil quality, aminoacid composition,sugar content, acid content (pH), sugar/acid ratio (Brix), polyphenols,starch content, nutritional quality, gluten content/index, energycontent, taste, etc.;and further comprising decreased undesired ingredients such as e.g. lessmycotoxines, less aflatoxines, geosmin level, phenolic aromas, lacchase,polyphenol oxidases and peroxidases, nitrate content etc.

Sustainable agriculture, comprising nutrient use efficiency, especiallynitrogen (N)-use efficiency, phosphours (P)-use efficiency, water useefficiency, improved transpiration, respiration and/or CO₂ assimilationrate, better nodulation, improved Ca-metabolism etc.

Delayed senescence, comprising improvement of plant physiology which ismanifested, for example, in a longer grain filling phase, leading tohigher yield, a longer duration of green leaf colouration of the plantand thus comprising colour (greening), water content, dryness etc.Accordingly, in the context of the present invention, it has been foundthat the specific inventive application of the active compoundcombination makes it possible to prolong the green leaf area duration,which delays the maturation (senescence) of the plant. The mainadvantage to the farmer is a longer grain filling phase leading tohigher yield. There is also an advantage to the farmer on the basis ofgreater flexibility in the harvesting time.

Therein “sedimentation value” is a measure for protein quality anddescribes according to Zeleny (Zeleny value) the degree of sedimentationof flour suspended in a lactic acid solution during a standard timeinterval. This is taken as a measure of the baking quality. Swelling ofthe gluten fraction of flour in lactic acid solution affects the rate ofsedimentation of a flour suspension. Both a higher gluten content and abetter gluten quality give rise to slower sedimentation and higherZeleny test values. The sedimentation value of flour depends on thewheat protein composition and is mostly correlated to the proteincontent, the wheat hardness, and the volume of pan and hearth loaves. Astronger correlation between loaf volume and Zeleny sedimentation volumecompared to SDS sedimentation volume could be due to the protein contentinfluencing both the volume and Zeleny value (Czech J. Food Sci. Vol.21, No. 3: 91-96, 2000).

Further the “falling number” as mentioned herein is a measure for thebaking quality of cereals, especially of wheat. The falling number testindicates that sprout damage may have occurred. It means that changes tothe physical properties of the starch portion of the wheat kernel hasalready happened. Therein, the falling number instrument analyzesviscosity by measuring the resistance of a flour and water paste to afalling plunger. The time (in seconds) for this to happen is known asthe falling number. The falling number results are recorded as an indexof enzyme activity in a wheat or flour sample and results are expressedin time as seconds. A high falling number (for example, above 300seconds) indicates minimal enzyme activity and sound quality wheat orflour. A low falling number (for example, below 250 seconds) indicatessubstantial enzyme activity and sprout-damaged wheat or flour.

The term “more developed root system”/“improved root growth” refers tolonger root system, deeper root growth, faster root growth, higher rootdry/fresh weight, higher root volume, larger root surface area, biggerroot diameter, higher root stability, more root branching, higher numberof root hairs, and/or more root tips and can be measured by analyzingthe root architecture with suitable methodologies and Image analysisprogrammes (e.g. WinRhizo).

The term “crop water use efficiency” refers technically to the mass ofagriculture produce per unit water consumed and economically to thevalue of product(s) produced per unit water volume consumed and can e.g.be measured in terms of yield per ha, biomass of the plants,thousand-kernel mass, and the number of ears per m2.

The term “nitrogen-use efficiency” refers technically to the mass ofagriculture produce per unit nitrogen consumed and economically to thevalue of product(s) produced per unit nitrogen consumed, reflectinguptake and utilization efficiency.

Improvement in greening/improved colour and improved photosyntheticefficiency as well as the delay of senescence can be measured withwell-known techniques such as a HandyPea system (Hansatech). Fv/Fm is aparameter widely used to indicate the maximum quantum efficiency ofphotosystem II (PSII). This parameter is widely considered to be aselective indication of plant photosynthetic performance with healthysamples typically achieving a maximum Fv/Fm value of approx. 0.85.Values lower than this will be observed if a sample has been exposed tosome type of biotic or abiotic stress factor which has reduced thecapacity for photochemical quenching of energy within PSII. Fv/Fm ispresented as a ratio of variable fluorescence (Fv) over the maximumfluorescence value (Fm). The Performance Index is essentially anindicator of sample vitality. (See e.g. Advanced Techniques in SoilMicrobiology, 2007, 11, 319-341; Applied Soil Ecology, 2000, 15,169-182.)

The improvement in greening/improved colour and improved photosyntheticefficiency as well as the delay of senescence can also be assessed bymeasurement of the net photosynthetic rate (Pn), measurement of thechlorophyll content, e.g. by the pigment extraction method of Zieglerand Ehle, measurement of the photochemical efficiency (Fv/Fm ratio),determination of shoot growth and final root and/or canopy biomass,determination of tiller density as well as of root mortality.

Within the context of the present invention preference is given toimproving plant physiology effects which are selected from the groupcomprising: enhanced root growth/more developed root system, improvedgreening, improved water use efficiency (correlating to reduced waterconsumption), improved nutrient use efficiency, comprising especiallyimproved nitrogen (N)-use efficiency, delayed senescence and enhancedyield.

Within the enhancement of yield preference is given as to an improvementin the sedimentation value and the falling number as well as to theimprovement of the protein and sugar content—especially with plantsselected from the group of cereals (preferably wheat).

Preferably the novel use of the fungicidal compositions of the presentinvention relates to a combined use of a) preventively and/or curativelycontrolling pathogenic fungi and/or nematodes, with or withoutresistance management, and b) at least one of enhanced root growth,improved greening, improved water use efficiency, delayed senescence andenhanced yield. From group b) enhancement of root system, water useefficiency and N-use efficiency is particularly preferred.

Seed Treatment

The invention further comprises a method for treating seed.

The invention further relates to seed which has been treated by one ofthe methods described in the previous paragraph. The inventive seeds areemployed in methods for the protection of seed from unwantedmicroorganisms. In these methods, seed treated with at least oneinventive active ingredient is used.

The inventive active ingredients or compositions are also suitable fortreating seed. A large part of the damage to crop plants caused byharmful organisms is triggered by the infection of the seed duringstorage or after sowing, and also during and after germination of theplant. This phase is particularly critical since the roots and shoots ofthe growing plant are particularly sensitive, and even minor damage mayresult in the death of the plant. There is therefore a great interest inprotecting the seed and the germinating plant by using appropriatecompositions.

The control of phytopathogenic fungi by treating the seed of plants hasbeen known for a long time and is the subject of constant improvements.However, the treatment of seed entails a series of problems which cannotalways be solved in a satisfactory manner. For instance, it is desirableto develop methods for protecting the seed and the germinating plant,which dispense with, or at least significantly reduce, the additionaldeployment of crop protection compositions after planting or afteremergence of the plants. It is also desirable to optimize the amount ofthe active ingredient used so as to provide the best possible protectionfor the seed and the germinating plant from attack by phytopathogenicfungi, but without damaging the plant itself by the active ingredientemployed. In particular, methods for the treatment of seed should alsotake account of the intrinsic fungicidal properties of transgenic plantsin order to achieve optimal protection of the seed and the germinatingplant with a minimum expenditure of crop protection compositions.

The present invention therefore also relates to a method for protectionof seed and germinating plants from attack by phytopathogenic fungi, bytreating the seed with an inventive composition. The invention likewiserelates to the use of the inventive compositions for treatment of seedto protect the seed and the germinating plant from phytopathogenicfungi. The invention further relates to seed which has been treated withan inventive composition for protection from phytopathogenic fungi.

The control of phytopathogenic fungi which damage plants post-emergenceis effected primarily by treating the soil and the above-ground parts ofplants with crop protection compositions. Owing to the concernsregarding a possible influence of the crop protection compositions onthe environment and the health of humans and animals, there are effortsto reduce the amount of active ingredients deployed.

One of the advantages of the present invention is that the particularsystemic properties of the inventive active ingredients and compositionsmean that treatment of the seed with these active ingredients andcompositions not only protects the seed itself, but also the resultingplants after emergence, from phytopathogenic fungi. In this way, theimmediate treatment of the crop at the time of sowing or shortlythereafter can be dispensed with.

It is likewise considered to be advantageous that the inventive activeingredients or compositions can especially also be used with transgenicseed, in which case the plant growing from this seed is capable ofexpressing a protein which acts against pests. By virtue of thetreatment of such seed with the inventive active ingredients orcompositions, merely the expression of the protein, for example aninsecticidal protein, can control certain pests. Surprisingly, a furthersynergistic effect can be observed in this case, which additionallyincreases the effectiveness for protection against attack by pests.

The inventive compositions are suitable for protecting seed of any plantvariety which is used in agriculture, in greenhouses, in forests or inhorticulture and viticulture. In particular, this is the seed of cereals(such as wheat, barley, rye, triticale, sorghum/millet and oats), maize,cotton, soya beans, rice, potatoes, sunflower, bean, coffee, beet (forexample sugar beet and fodder beet), peanut, oilseed rape, poppy, olive,coconut, cocoa, sugar cane, tobacco, vegetables (such as tomato,cucumbers, onions and lettuce), turf and ornamentals (see also below).The treatment of the seed of cereals (such as wheat, barley, rye,triticale and oats), maize and rice is of particular significance.

As also described below, the treatment of transgenic seed with theinventive active ingredients or compositions is of particularsignificance. This relates to the seed of plants containing at least oneheterologous gene. Definition and examples of suitable heterologousgenes are given below.

In the context of the present invention, the inventive composition isapplied to the seed alone or in a suitable formulation. Preferably, theseed is treated in a state in which it is sufficiently stable for nodamage to occur in the course of treatment. In general, the seed can betreated at any time between harvest and sowing. It is customary to useseed which has been separated from the plant and freed from cobs,shells, stalks, coats, hairs or the flesh of the fruits. For example, itis possible to use seed which has been harvested, cleaned and dried downto a moisture content of less than 15% by weight. Alternatively, it isalso possible to use seed which, after drying, for example, has beentreated with water and then dried again.

When treating the seed, care must generally be taken that the amount ofthe inventive composition applied to the seed and/or the amount offurther additives is selected such that the germination of the seed isnot impaired, or that the resulting plant is not damaged. This has to beborne in mind in particular in the case of active ingredients which canhave phytotoxic effects at certain application rates.

The inventive compositions can be applied directly, i.e. withoutcontaining any other components and without having been diluted. Ingeneral, it is preferable to apply the compositions to the seed in theform of a suitable formulation. Suitable formulations and methods forseed treatment are known to those skilled in the art and are described,for example, in the following documents: U.S. Pat. No. 4,272,417, U.S.Pat. No. 4,245,432, U.S. Pat. No. 4,808,430, U.S. Pat. No. 5,876,739, US2003/0176428 A1, WO 2002/080675, WO 2002/028186.

The active ingredients usable in accordance with the invention can beconverted to the customary seed dressing formulations, such assolutions, emulsions, suspensions, powders, foams, slurries or othercoating compositions for seed, and also ULV formulations.

These formulations are prepared in a known manner, by mixing the activeingredients with customary additives, for example customary extendersand also solvents or diluents, dyes, wetting agents, dispersants,emulsifiers, antifoams, preservatives, secondary thickeners, adhesives,gibberellins and also water.

Useful dyes which may be present in the seed dressing formulationsusable in accordance with the invention are all dyes which are customaryfor such purposes. It is possible to use either pigments, which aresparingly soluble in water, or dyes, which are soluble in water.Examples include the dyes known by the names Rhodamine B, C.I. PigmentRed 112 and C.I. Solvent Red 1.

Useful wetting agents which may be present in the seed dressingformulations usable in accordance with the invention are all substanceswhich promote wetting and which are conventionally used for theformulation of active agrochemical ingredients. Preference is given tousing alkyl naphthalenesulphonates, such as diisopropyl or diisobutylnaphthalenesulphonates.

Useful dispersants and/or emulsifiers which may be present in the seeddressing formulations usable in accordance with the invention are allnonionic, anionic and cationic dispersants conventionally used for theformulation of active agrochemical ingredients. Usable with preferenceare nonionic or anionic dispersants or mixtures of nonionic or anionicdispersants. Suitable nonionic dispersants include especially ethyleneoxide/propylene oxide block polymers, alkylphenol polyglycol ethers andtristryrylphenol polyglycol ether, and the phosphated or sulphatedderivatives thereof. Suitable anionic dispersants are especiallylignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehydecondensates.

Antifoams which may be present in the seed dressing formulations usablein accordance with the invention are all foam-inhibiting substancesconventionally used for the formulation of active agrochemicalingredients. Silicone antifoams and magnesium stearate can be used withpreference.

Preservatives which may be present in the seed dressing formulationsusable in accordance with the invention are all substances usable forsuch purposes in agrochemical compositions. Examples includedichlorophene and benzyl alcohol hemiformal.

Secondary thickeners which may be present in the seed dressingformulations usable in accordance with the invention are all substancesusable for such purposes in agrochemical compositions. Preferredexamples include cellulose derivatives, acrylic acid derivatives,xanthan, modified clays and finely divided silica.

Adhesives which may be present in the seed dressing formulations usablein accordance with the invention are all customary binders usable inseed dressing products. Preferred examples include polyvinylpyrrolidone,polyvinyl acetate, polyvinyl alcohol and tylose.

The gibberellins which may be present in the seed dressing formulationsusable in accordance with the invention may preferably be gibberellinsA1, A3 (=gibberellic acid), A4 and A7; particular preference is given tousing gibberellic acid. The gibberellins are known (cf. R. Wegler“Chemie der Pflanzenschutz- and Schädlings-bekämpfungsmittel” [Chemistryof the Crop Protection Compositions and Pesticides], vol. 2, SpringerVerlag, 1970, p. 401-412).

The seed dressing formulations usable in accordance with the inventioncan be used, either directly or after previously having been dilutedwith water, for the treatment of a wide range of different seed,including the seed of transgenic plants. In this case, additionalsynergistic effects may also occur in interaction with the substancesformed by expression.

For treatment of seed with the seed dressing formulations usable inaccordance with the invention, or the preparations prepared therefrom byadding water, all mixing units usable customarily for the seed dressingare useful. Specifically, the procedure in the seed dressing is to placethe seed into a mixer, to add the particular desired amount of seeddressing formulations, either as such or after prior dilution withwater, and to mix everything until the formulation is distributedhomogeneously on the seed. If appropriate, this is followed by a dryingprocess.

Mycotoxins

In addition, the inventive treatment can reduce the mycotoxin content inthe harvested material and the foods and feeds prepared therefrom.Mycotoxins include particularly, but not exclusively, the following:deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxin,fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol(DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins,patulin, ergot alkaloids and aflatoxins which can be produced, forexample, by the following fungi: Fusarium spec., such as F. acuminatum,F. asiaticum, F. avenaceum, F. crookwellense, F. culmorum, F.graminearum (Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F.oxysporum, F. proliferatum, F. poae, F. pseudograminearum, F.sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F.langsethiae, F. sub glutinans, F. tricincturn, F. verticillioides etc.,and also by Aspergillus spec., such as A. flavus, A. parasiticus, A.nomius, A. ochraceus, A. clavatus, A. terreus, A. versicolor,Penicillium spec., such as P. verrucosum, P. viridicatum, P. citrinum,P. expansum, P. claviforme, P. roqueforti, Claviceps spec., such as C.purpurea, C. fusiformis, C. paspali, C. africana, Stachybotrys spec. andothers.

Material Protection

The inventive active ingredients or compositions can also be used in theprotection of materials, for protection of industrial materials againstattack and destruction by unwanted microorganisms, for example fungi andinsects.

In addition, the inventive compounds can be used as antifoulingcompositions, alone or in combinations with other active ingredients.

Industrial materials in the present context are understood to meaninanimate materials which have been prepared for use in industry. Forexample, industrial materials which are to be protected by inventiveactive ingredients from microbial alteration or destruction may beadhesives, glues, paper, wallpaper and board/cardboard, textiles,carpets, leather, wood, fibers and tissues, paints and plastic articles,cooling lubricants and other materials which can be infected with ordestroyed by microorganisms. Parts of production plants and buildings,for example cooling-water circuits, cooling and heating systems andventilation and air-conditioning units, which may be impaired by theproliferation of microorganisms may also be mentioned within the scopeof the materials to be protected. Industrial materials within the scopeof the present invention preferably include adhesives, sizes, paper andcard, leather, wood, paints, cooling lubricants and heat transferfluids, more preferably wood.

The inventive active ingredients or compositions may prevent adverseeffects, such as rotting, decay, discoloration, decoloration orformation of mould.

In the case of treatment of wood the compounds/compositions according tothe invention may also be used against fungal diseases liable to grow onor inside timber. The term “timber” means all types of species of wood,and all types of working of this wood intended for construction, forexample solid wood, high-density wood, laminated wood, and plywood. Themethod for treating timber according to the invention mainly consists incontacting one or more compounds according to the invention or acomposition according to the invention; this includes for example directapplication, spraying, dipping, injection or any other suitable means.

In addition, the inventive compounds can be used to protect objectswhich come into contact with saltwater or brackish water, especiallyhulls, screens, nets, buildings, moorings and signalling systems, fromfouling.

The inventive method for controlling unwanted fungi can also be employedfor protecting storage goods. Storage goods are understood to meannatural substances of vegetable or animal origin or processed productsthereof which are of natural origin, and for which long-term protectionis desired. Storage goods of vegetable origin, for example plants orplant parts, such as stems, leaves, tubers, seeds, fruits, grains, canbe protected freshly harvested or after processing by (pre)drying,moistening, comminuting, grinding, pressing or roasting. Storage goodsalso include timber, both unprocessed, such as construction timber,electricity poles and barriers, or in the form of finished products,such as furniture. Storage goods of animal origin are, for example,hides, leather, furs and hairs. The inventive active ingredients mayprevent adverse effects, such as rotting, decay, discoloration,decoloration or formation of mould.

Microorganisms capable of degrading or altering the industrial materialsinclude, for example, bacteria, fungi, yeasts, algae and slimeorganisms. The inventive active ingredients preferably act againstfungi, especially moulds, wood-discoloring and wood-destroying fungi(Ascomycetes, Basidiomycetes, Deuteromycetes and Zygomycetes), andagainst slime organisms and algae. Examples include microorganisms ofthe following genera: Alternaria, such as Alternaria tenuis;Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomiumglobosum; Coniophora, such as Coniophora puetana; Lentinus, such asLentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus,such as Polyporus versicolor; Aureobasidium, such as Aureobasidiumpullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma,such as Trichoderma viride; Ophiostoma spp., Ceratocystis spp., Humicolaspp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp.,Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp.,Cladosporium spp., Paecilomyces spp. Mucor spp., Escherichia, such asEscherichia coli; Pseudomonas, such as Pseudomonas aeruginosa;Staphylococcus, such as Staphylococcus aureus, Candida spp. andSaccharomyces spp., such as Saccharomyces cerevisae.

Antimycotic Activity

In addition, the inventive active ingredients also have very goodantimycotic activity. They have a very broad antimycotic activityspectrum, especially against dermatophytes and yeasts, moulds anddiphasic fungi (for example against Candida species, such as C.albicans, C. glabrata), and Epidermophyton floccosum, Aspergillusspecies, such as A. niger and A. fumigatus, Trichophyton species, suchas T. mentagrophytes, Microsporon species such as M. canis and M.audouinii. The list of these fungi by no means constitutes a restrictionof the mycotic spectrum covered, and is merely of illustrativecharacter.

The inventive active ingredients can therefore be used both in medicaland in non-medical applications.

GMO

As already mentioned above, it is possible to treat all plants and theirparts in accordance with the invention. In a preferred embodiment, wildplant species and plant cultivars, or those obtained by conventionalbiological breeding methods, such as crossing or protoplast fusion, andalso parts thereof, are treated. In a further preferred embodiment,transgenic plants and plant cultivars obtained by genetic engineeringmethods, if appropriate in combination with conventional methods(Genetically Modified Organisms), and parts thereof are treated. Theterms “parts” or “parts of plants” or “plant parts” have been explainedabove. More preferably, plants of the plant cultivars which arecommercially available or are in use are treated in accordance with theinvention. Plant cultivars are understood to mean plants which have newproperties (“traits”) and have been obtained by conventional breeding,by mutagenesis or by recombinant DNA techniques. They can be cultivars,varieties, bio- or genotypes.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants ofwhich a heterologous gene has been stably integrated into genome. Theexpression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for example,antisense technology, cosuppression technology, RNAinterference—RNAi—technology or microRNA—miRNA—technology). Aheterologous gene that is located in the genome is also called atransgene. A transgene that is defined by its particular location in theplant genome is called a transformation or transgenic event.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active compounds and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf color, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which exceed theeffects which were actually to be expected.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are also suitable for mobilizing the defense system ofthe plant against attack by unwanted microorganisms. This may, ifappropriate, be one of the reasons of the enhanced activity of thecombinations according to the invention, for example against fungi.Plant-strengthening (resistance-inducing) substances are to beunderstood as meaning, in the present context, those substances orcombinations of substances which are capable of stimulating the defensesystem of plants in such a way that, when subsequently inoculated withunwanted microorganisms, the treated plants display a substantial degreeof resistance to these microorganisms. In the present case, unwantedmicroorganisms are to be understood as meaning phytopathogenic fungi,bacteria and viruses. Thus, the substances according to the inventioncan be employed for protecting plants against attack by theabovementioned pathogens within a certain period of time after thetreatment. The period of time within which protection is effectedgenerally extends from 1 to 10 days, preferably 1 to 7 days, after thetreatment of the plants with the active compounds.

Plants and plant cultivars which are preferably to be treated accordingto the invention include all plants which have genetic material whichimpart particularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstresses, i.e. said plants show a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode or insect resistant plants are described in e.g.U.S. patent application Ser. Nos. 11/765,491, 11/765,494, 10/926,819,10/782,020, 12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904,11/396,808, 12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886,12/364,335, 11/763,947, 12/252,453, 12/209,354, 12/491,396, 12/497,221,12/644,632, 12/646,004, 12/701,058, 12/718,059, 12/721,595, 12/638,591.

Plants and plant cultivars which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, flooding,increased soil salinity, increased mineral exposure, ozone exposure,high light exposure, limited availability of nitrogen nutrients, limitedavailability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to theinvention, are those plants characterized by enhanced yieldcharacteristics. Increased yield in said plants can be the result of,for example, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including but not limited to, early flowering, floweringcontrol for hybrid seed production, seedling vigor, plant size,internode number and distance, root growth, seed size, fruit size, podsize, pod or ear number, seed number per pod or ear, seed mass, enhancedseed filling, reduced seed dispersal, reduced pod dehiscence and lodgingresistance. Further yield traits include seed composition, such ascarbohydrate content, protein content, oil content and composition,nutritional value, reduction in anti-nutritional compounds, improvedprocessability and better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristic of heterosis or hybrid vigorwhich results in generally higher yield, vigor, health and resistancetowards biotic and abiotic stresses). Such plants are typically made bycrossing an inbred male-sterile parent line (the female parent) withanother inbred male-fertile parent line (the male parent). Hybrid seedis typically harvested from the male sterile plants and sold to growers.Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling, i.e. the mechanical removal of the male reproductive organs(or males flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plantsit is typically useful to ensure that male fertility in the hybridplants is fully restored. This can be accomplished by ensuring that themale parents have appropriate fertility restorer genes which are capableof restoring the male fertility in hybrid plants that contain thegenetic determinants responsible for male-sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO05/002324, WO 06/021972 and U.S. Pat. No. 6,229,072). However, geneticdeterminants for male sterility can also be located in the nucleargenome. Male sterile plants can also be obtained by plant biotechnologymethods such as genetic engineering. A particularly useful means ofobtaining male-sterile plants is described in WO 89/10396 in which, forexample, a ribonuclease such as barnase is selectively expressed in thetapetum cells in the stamens. Fertility can then be restored byexpression in the tapetum cells of a ribonuclease inhibitor such asbarstar (e.g. WO 91/02069).

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-resistant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.Plants can be made tolerant to glyphosate through different means. Forexample, glyphosate-tolerant plants can be obtained by transforming theplant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphatesynthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutantCT7) of the bacterium Salmonella typhimurium (Science 1983, 221,370-371), the CP4 gene of the bacterium Agrobacterium sp. (Curr. TopicsPlant Physiol. 1992, 7, 139-145), the genes encoding a Petunia EPSPS(Science 1986, 233, 478-481), a Tomato EPSPS (J. Biol. Chem. 1988, 263,4280-4289), or an Eleusine EPSPS (WO 01/66704). It can also be a mutatedEPSPS as described in for example EP 0837944, WO 00/66746, WO 00/66747or WO 02/26995. Glyphosate-tolerant plants can also be obtained byexpressing a gene that encodes a glyphosate oxido-reductase enzyme asdescribed in U.S. Pat. No. 5,776,760 and U.S. Pat. No. 5,463,175.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyl transferase enzyme as described in forexample WO 02/036782, WO 03/092360, WO 2005/012515 and WO 2007/024782.Glyphosate-tolerant plants can also be obtained by selecting plantscontaining naturally-occurring mutations of the above-mentioned genes,as described in for example WO 01/024615 or WO 03/013226. Plantsexpressing EPSPS genes that confer glyphosate tolerance are described ine.g. U.S. patent application Ser. Nos. 11/517,991, 10/739,610,12/139,408, 12/352,532, 11/312,866, 11/315,678, 12/421,292, 11/400,598,11/651,752, 11/681,285, 11/605,824, 12/468,205, 11/760,570, 11/762,526,11/769,327, 11/769,255, 11/943,801 or 12/362,774. Plants comprisingother genes that confer glyphosate tolerance, such as decarboxylasegenes, are described in e.g. U.S. patent application Ser. Nos.11/588,811, 11/185,342, 12/364,724, 11/185,560 or 12/423,926.

Other herbicide resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition, e.g. described in U.S.patent application Ser. No. 11/760,602. One such efficient detoxifyingenzyme is an enzyme encoding a phosphinothricin acetyltransferase (suchas the bar or pat protein from Streptomyces species). Plants expressingan exogenous phosphinothricin acetyltransferase are for exampledescribed in U.S. Pat. Nos. 5,561,236; 5,648,477; 5,646,024; 5,273,894;5,637,489; 5,276,268; 5,739,082; 5,908,810 and 7,112,665.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). HPPD is an enzyme that catalyze the reaction in whichparahydroxyphenylpyruvate (HPP) is transformed into homogentisate.Plants tolerant to HPPD-inhibitors can be transformed with a geneencoding a naturally-occurring resistant HPPD enzyme, or a gene encodinga mutated or chimeric HPPD enzyme as described in WO 96/38567, WO99/24585, WO 99/24586, WO 09/144079, WO 02/046387, or U.S. Pat. No.6,768,044. Tolerance to HPPD-inhibitors can also be obtained bytransforming plants with genes encoding certain enzymes enabling theformation of homogentisate despite the inhibition of the native HPPDenzyme by the HPPD-inhibitor. Such plants and genes are described in WO99/34008 and WO 02/36787. Tolerance of plants to HPPD inhibitors canalso be improved by transforming plants with a gene encoding an enzymehaving prephenate deshydrogenase (PDH) activity in addition to a geneencoding an HPPD-tolerant enzyme, as described in WO 04/024928. Further,plants can be made more tolerant to HPPD-inhibitor herbicides by addinginto their genome a gene encoding an enzyme capable of metabolizing ordegrading HPPD inhibitors, such as the CYP450 enzymes shown in WO2007/103567 and WO 2008/150473.

Still further herbicide resistant plants are plants that are madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitorsinclude, for example, sulfonylurea, imidazolinone, triazolopyrimidines,pryimidinyoxy-(thio)benzoates, and/or sulfonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides, as described for examplein Tranel and Wright (Weed Science 2002, 50, 700-712), but also, in U.S.Pat. Nos. 5,605,011, 5,378,824, 5,141,870, and 5,013,659. The productionof sulfonylurea-tolerant plants and imidazolinone-tolerant plants isdescribed in U.S. Pat. Nos. 5,605,011; 5,013,659; 5,141,870; 5,767,361;5,731,180; 5,304,732; 4,761,373; 5,331,107; 5,928,937; and 5,378,824;and WO 96/33270. Other imidazolinone-tolerant plants are also describedin for example WO 2004/040012, WO 2004/106529, WO 2005/020673, WO2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351, and WO2006/060634. Further sulfonylurea- and imidazolinone-tolerant plants arealso described in for example WO 2007/024782 and U.S. Patent Application61/288,958.

Other plants tolerant to imidazolinone and/or sulfonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding as described for examplefor soybeans in U.S. Pat. No. 5,084,082, for rice in WO 97/41218, forsugar beet in U.S. Pat. No. 5,773,702 and WO 99/057965, for lettuce inU.S. Pat. No. 5,198,599, or for sunflower in WO 01/065922.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes anyplant containing at least one transgene comprising a coding sequenceencoding:

-   1) an insecticidal crystal protein from Bacillus thuringiensis or an    insecticidal portion thereof, such as the insecticidal crystal    proteins listed by Crickmore et al. (1998, Microbiology and    Molecular Biology Reviews, 62: 807-813), updated by Crickmore et    al. (2005) at the Bacillus thuringiensis toxin nomenclature, online    at: http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/BY), or    insecticidal portions thereof, e.g., proteins of the Cry protein    classes Cry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab, Cry3Aa,    or Cry3Bb or insecticidal portions thereof (e.g. EP-A 1 999 141 and    WO 2007/107302), or such proteins encoded by synthetic genes as e.g.    described in and U.S. patent application Ser. No. 12/249,016; or-   2) a crystal protein from Bacillus thuringiensis or a portion    thereof which is insecticidal in the presence of a second other    crystal protein from Bacillus thuringiensis or a portion thereof,    such as the binary toxin made up of the Cry34 and Cry35 crystal    proteins (Nat. Biotechnol. 2001, 19, 668-72; Applied Environm.    Microbiol. 2006, 71, 1765-1774) or the binary toxin made up of the    Cry1A or Cry1F proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins    (U.S. patent application Ser. No. 12/214,022 and EP-A 2 300 618); or-   3) a hybrid insecticidal protein comprising parts of different    insecticidal crystal proteins from Bacillus thuringiensis, such as a    hybrid of the proteins of 1) above or a hybrid of the proteins of 2)    above, e.g., the Cry1A.105 protein produced by corn event MON89034    (WO 2007/027777); or-   4) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes introduced into the encoding DNA during cloning    or transformation, such as the Cry3Bbl protein in corn events MON863    or MON88017, or the Cry3A protein in corn event MIR604; or-   5) an insecticidal secreted protein from Bacillus thuringiensis or    Bacillus cereus, or an insecticidal portion thereof, such as the    vegetative insecticidal (VIP) proteins listed at:    http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html,    e.g., proteins from the VIP3Aa protein class; or-   6) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a second secreted protein    from Bacillus thuringiensis or B. cereus, such as the binary toxin    made up of the VIP1A and VIP2A proteins (WO 94/21795); or-   7) a hybrid insecticidal protein comprising parts from different    secreted proteins from Bacillus thuringiensis or Bacillus cereus,    such as a hybrid of the proteins in 1) above or a hybrid of the    proteins in 2) above; or-   8) a protein of any one of 5) to 7) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes introduced into the encoding DNA during cloning    or transformation (while still encoding an insecticidal protein),    such as the VIP3Aa protein in cotton event COT102; or-   9) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a crystal protein from    Bacillus thuringiensis, such as the binary toxin made up of VIP3 and    Cry1A or Cry1F (U.S. Patent Applications 61/126,083 and 61/195,019),    or the binary toxin made up of the VIP3 protein and the Cry2Aa or    Cry2Ab or Cry2Ae proteins (U.S. patent application Ser. No.    12/214,022 and EP-A 2 300 618).-   10) a protein of 9) above wherein some, particularly 1 to 10, amino    acids have been replaced by another amino acid to obtain a higher    insecticidal activity to a target insect species, and/or to expand    the range of target insect species affected, and/or because of    changes introduced into the encoding DNA during cloning or    transformation (while still encoding an insecticidal protein)

Of course, an insect-resistant transgenic plant, as used herein, alsoincludes any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 10. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 10, to expand the range oftarget insect species affected when using different proteins directed atdifferent target insect species, or to delay insect resistancedevelopment to the plants by using different proteins insecticidal tothe same target insect species but having a different mode of action,such as binding to different receptor binding sites in the insect.

An “insect-resistant transgenic plant”, as used herein, further includesany plant containing at least one transgene comprising a sequenceproducing upon expression a double-stranded RNA which upon ingestion bya plant insect pest inhibits the growth of this insect pest, asdescribed e.g. in WO 2007/080126, WO 2006/129204, WO 2007/074405, WO2007/080127 and WO 2007/035650.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

-   1) plants which contain a transgene capable of reducing the    expression and/or the activity of poly(ADPribose) polymerase (PARP)    gene in the plant cells or plants as described in WO 00/04173, WO    2006/045633, EP-A 1 807 519, or EP-A 2 018 431.-   2) plants which contain a stress tolerance enhancing transgene    capable of reducing the expression and/or the activity of the PARG    encoding genes of the plants or plants cells, as described e.g. in    WO 2004/090140.-   3) plants which contain a stress tolerance enhancing transgene    coding for a plant-functional enzyme of the nicotineamide adenine    dinucleotide salvage synthesis pathway including nicotinamidase,    nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide    adenyl transferase, nicotinamide adenine dinucleotide synthetase or    nicotine amide phosphorybosyltransferase as described e.g. in EP-A 1    794 306, WO 2006/133827, WO 2007/107326, EP-A 1 999 263, or WO    2007/107326.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage-stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as:

-   1) transgenic plants which synthesize a modified starch, which in    its physical-chemical characteristics, in particular the amylose    content or the amylose/amylopectin ratio, the degree of branching,    the average chain length, the side chain distribution, the viscosity    behaviour, the gelling strength, the starch grain size and/or the    starch grain morphology, is changed in comparison with the    synthesised starch in wild type plant cells or plants, so that this    is better suited for special applications. Said transgenic plants    synthesizing a modified starch are disclosed, for example, in EP-A 0    571 427, WO 95/04826, EP-A 0 719 338, WO 96/15248, WO 96/19581, WO    96/27674, WO 97/11188, WO 97/26362, WO 97/32985, WO 97/42328, WO    97/44472, WO 97/45545, WO 98/27212, WO 98/40503, WO 99/58688, WO    99/58690, WO 99/58654, WO 00/08184, WO 00/08185, WO 00/08175, WO    00/28052, WO 00/77229, WO 01/12782, WO 01/12826, WO 02/101059, WO    03/071860, WO 04/056999, WO 05/030942, WO 2005/030941, WO    2005/095632, WO 2005/095617, WO 2005/095619, WO 2005/095618, WO    2005/123927, WO 2006/018319, WO 2006/103107, WO 2006/108702, WO    2007/009823, WO 00/22140, WO 2006/063862, WO 2006/072603, WO    02/034923, WO 2008/017518, WO 2008/080630, WO 2008/080631, WO    2008/090008, WO 01/14569, WO 02/79410, WO 03/33540, WO 2004/078983,    WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145, WO 99/12950, WO    99/66050, WO 99/53072, U.S. Pat. No. 6,734,341, WO 00/11192, WO    98/22604, WO 98/32326, WO 01/98509, WO 01/98509, WO 2005/002359,    U.S. Pat. No. 5,824,790, U.S. Pat. No. 6,013,861, WO 94/04693, WO    94/09144, WO 94/11520, WO 95/35026, WO 97/20936, WO 2010/012796, WO    2010/003701,-   2) transgenic plants which synthesize non starch carbohydrate    polymers or which synthesize non starch carbohydrate polymers with    altered properties in comparison to wild type plants without genetic    modification. Examples are plants producing polyfructose, especially    of the inulin and levan-type, as disclosed in EP-A 0 663 956, WO    96/01904, WO 96/21023, WO 98/39460, and WO 99/24593, plants    producing alpha-1,4-glucans as disclosed in WO 95/31553, US    2002031826, U.S. Pat. No. 6,284,479, U.S. Pat. No. 5,712,107, WO    97/47806, WO 97/47807, WO 97/47808 and WO 00/14249, plants producing    alpha-1,6 branched alpha-1,4-glucans, as disclosed in WO 00/73422,    plants producing alternan, as disclosed in e.g. WO 00/47727, WO    00/73422, U.S. Pat. No. 5,908,975 and EP-A 0 728 213,-   3) transgenic plants which produce hyaluronan, as for example    disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO    2007/039316, JP-A 2006-304779, and WO 2005/012529.-   4) transgenic plants or hybrid plants, such as onions with    characteristics such as ‘high soluble solids content’, ‘low    pungency’ (LP) and/or ‘long storage’ (LS), as described in U.S.    patent application Ser. No. 12/020,360.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as cotton plants, with altered fibercharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants contain a mutation imparting such alteredfiber characteristics and include:

-   a) Plants, such as cotton plants, containing an altered form of    cellulose synthase genes as described in WO 98/00549.-   b) Plants, such as cotton plants, containing an altered form of rsw2    or rsw3 homologous nucleic acids as described in WO 2004/053219.-   c) Plants, such as cotton plants, with increased expression of    sucrose phosphate synthase as described in WO 01/17333.-   d) Plants, such as cotton plants, with increased expression of    sucrose synthase as described in WO 02/45485.-   e) Plants, such as cotton plants, wherein the timing of the    plasmodesmatal gating at the basis of the fiber cell is altered,    e.g. through downregulation of fiber-selective β-1,3-glucanase as    described in WO 2005/017157, or as described in WO 2009/143995.-   f) Plants, such as cotton plants, having fibers with altered    reactivity, e.g. through the expression of    N-acetylglucosaminetransferase gene including nodC and chitin    synthase genes as described in WO 2006/136351.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered oil profile characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered oil profile characteristics and include:

-   a) Plants, such as oilseed rape plants, producing oil having a high    oleic acid content as described e.g. in U.S. Pat. No. 5,969,169,    U.S. Pat. No. 5,840,946 or U.S. Pat. No. 6,323,392 or U.S. Pat. No.    6,063,947-   b) Plants such as oilseed rape plants, producing oil having a low    linolenic acid content as described in U.S. Pat. No. 6,270,828, U.S.    Pat. No. 6,169,190, or U.S. Pat. No. 5,965,755-   c) Plant such as oilseed rape plants, producing oil having a low    level of saturated fatty acids as described e.g. in U.S. Pat. No.    5,434,283 or U.S. patent application Ser. No. 12/668,303

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered seed shattering characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered seed shattering characteristics andinclude plants such as oilseed rape plants with delayed or reduced seedshattering as described in U.S. Patent Application 61/135,230, WO2009/068313 and WO 2010/006732.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as Tobacco plants, with alteredposttranslational protein modification patterns, for example asdescribed in WO 2010/121818 and WO 2010/145846.

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, orcombination of transformation events, that are the subject of petitionsfor non-regulated status, in the United States of America, to the Animaland Plant Health Inspection Service (APHIS) of the United StatesDepartment of Agriculture (USDA) whether such petitions are granted orare still pending. At any time this information is readily availablefrom APHIS (4700 River Road, Riverdale, Md. 20737, USA), for instance onits internet site (URL http://www.aphis.usda.gov/brs/not_reg.html). Onthe filing date of this application the petitions for nonregulatedstatus that were pending with APHIS or granted by APHIS were those whichcontains the following information:

-   -   Petition: the identification number of the petition. Technical        descriptions of the transformation events can be found in the        individual petition documents which are obtainable from APHIS,        for example on the APHIS website, by reference to this petition        number. These descriptions are herein incorporated by reference.    -   Extension of Petition: reference to a previous petition for        which an extension is requested.    -   Institution: the name of the entity submitting the petition.    -   Regulated article: the plant species concerned.    -   Transgenic phenotype: the trait conferred to the plants by the        transformation event.    -   Transformation event or line: the name of the event or events        (sometimes also designated as lines or lines) for which        nonregulated status is requested.    -   APHIS documents: various documents published by APHIS in        relation to the Petition and which can be requested with APHIS.

Additional particularly useful plants containing single transformationevents or combinations of transformation events are listed for examplein the databases from various national or regional regulatory agencies(see for example http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, or acombination of transformation events, and that are listed for example inthe databases for various national or regional regulatory agenciesincluding Event 1143-14A (cotton, insect control, not deposited,described in WO 2006/128569); Event 1143-51B (cotton, insect control,not deposited, described in WO 2006/128570); Event 1445 (cotton,herbicide tolerance, not deposited, described in USA 2002-120964 or WO02/034946); Event 17053 (rice, herbicide tolerance, deposited asPTA-9843, described in WO 2010/117737); Event 17314 (rice, herbicidetolerance, deposited as PTA-9844, described in WO 2010/117735); Event281-24-236 (cotton, insect control-herbicide tolerance, deposited asPTA-6233, described in WO 2005/103266 or US-A 2005-216969); Event3006-210-23 (cotton, insect control-herbicide tolerance, deposited asPTA-6233, described in US-A 2007-143876 or WO 2005/103266); Event 3272(corn, quality trait, deposited as PTA-9972, described in WO 2006/098952or US-A 2006-230473); Event 40416 (corn, insect control-herbicidetolerance, deposited as ATCC PTA-11508, described in WO 2011/075593);Event 43A47 (corn, insect control-herbicide tolerance, deposited as ATCCPTA-11509, described in WO 2011/075595); Event 5307 (corn, insectcontrol, deposited as ATCC PTA-9561, described in WO 2010/077816); EventASR-368 (bent grass, herbicide tolerance, deposited as ATCC PTA-4816,described in US-A 2006-162007 or WO 2004/053062); Event B16 (corn,herbicide tolerance, not deposited, described in US-A 2003-126634);Event BPS-CV127-9 (soybean, herbicide tolerance, deposited as NCIMB No.41603, described in WO 2010/080829); Event CE43-67B (cotton, insectcontrol, deposited as DSM ACC2724, described in US-A 2009-217423 orWO2006/128573); Event CE44-69D (cotton, insect control, not deposited,described in US-A 2010-0024077); Event CE44-69D (cotton, insect control,not deposited, described in WO 2006/128571); Event CE46-02A (cotton,insect control, not deposited, described in WO 2006/128572); EventCOT102 (cotton, insect control, not deposited, described in US-A2006-130175 or WO 2004/039986); Event COT202 (cotton, insect control,not deposited, described in US-A 2007-067868 or WO 2005/054479); EventCOT203 (cotton, insect control, not deposited, described in WO2005/054480); Event DAS40278 (corn, herbicide tolerance, deposited asATCC PTA-10244, described in WO 2011/022469); Event DAS-59122-7 (corn,insect control-herbicide tolerance, deposited as ATCC PTA 11384,described in US-A 2006-070139); Event DAS-59132 (corn, insectcontrol-herbicide tolerance, not deposited, described in WO2009/100188); Event DAS68416 (soybean, herbicide tolerance, deposited asATCC PTA-10442, described in WO 2011/066384 or WO 2011/066360); EventDP-098140-6 (corn, herbicide tolerance, deposited as ATCC PTA-8296,described in US-A 2009-137395 or WO 2008/112019); Event DP-305423-1(soybean, quality trait, not deposited, described in US-A 2008-312082 orWO 2008/054747); Event DP-32138-1 (corn, hybridization system, depositedas ATCC PTA-9158, described in US-A 2009-0210970 or WO 2009/103049);Event DP-356043-5 (soybean, herbicide tolerance, deposited as ATCCPTA-8287, described in US-A 2010-0184079 or WO 2008/002872); Event EE-1(brinjal, insect control, not deposited, described in WO 2007/091277);Event FI117 (corn, herbicide tolerance, deposited as ATCC 209031,described in US-A 2006-059581 or WO 98/044140); Event GA21 (corn,herbicide tolerance, deposited as ATCC 209033, described in US-A2005-086719 or WO 98/044140); Event GG25 (corn, herbicide tolerance,deposited as ATCC 209032, described in US-A 2005-188434 or WO98/044140); Event GHB119 (cotton, insect control-herbicide tolerance,deposited as ATCC PTA-8398, described in WO 2008/151780); Event GHB614(cotton, herbicide tolerance, deposited as ATCC PTA-6878, described inUS-A 2010-050282 or WO 2007/017186); Event GJ11 (corn, herbicidetolerance, deposited as ATCC 209030, described in US-A 2005-188434 or WO98/044140); Event GM RZ13 (sugar beet, virus resistance, deposited asNCIMB-41601, described in WO 2010/076212); Event H7-1 (sugar beet,herbicide tolerance, deposited as NCIMB 41158 or NCIMB 41159, describedin US-A 2004-172669 or WO 2004/074492); Event JOPLIN1 (wheat, diseasetolerance, not deposited, described in US-A 2008-064032); Event LL27(soybean, herbicide tolerance, deposited as NCIMB41658, described in WO2006/108674 or US-A 2008-320616); Event LL55 (soybean, herbicidetolerance, deposited as NCIMB 41660, described in WO 2006/108675 or US-A2008-196127); Event LLcotton25 (cotton, herbicide tolerance, depositedas ATCC PTA-3343, described in WO 03/013224 or US-A 2003-097687); EventLLRICE06 (rice, herbicide tolerance, deposited as ATCC-23352, describedin U.S. Pat. No. 6,468,747 or WO 00/026345); Event LLRICE601 (rice,herbicide tolerance, deposited as ATCC PTA-2600, described in US-A2008-2289060 or WO 00/026356); Event LY038 (corn, quality trait,deposited as ATCC PTA-5623, described in US-A 2007-028322 or WO2005/061720); Event MIR162 (corn, insect control, deposited as PTA-8166,described in US-A 2009-300784 or WO 2007/142840); Event MIR604 (corn,insect control, not deposited, described in US-A 2008-167456 or WO2005/103301); Event MON15985 (cotton, insect control, deposited as ATCCPTA-2516, described in US-A 2004-250317 or WO 02/100163); Event MON810(corn, insect control, not deposited, described in US-A 2002-102582);Event MON863 (corn, insect control, deposited as ATCC PTA-2605,described in WO 2004/011601 or US-A 2006-095986); Event MON87427 (corn,pollination control, deposited as ATCC PTA-7899, described in WO2011/062904); Event MON87460 (corn, stress tolerance, deposited as ATCCPTA-8910, described in WO 2009/111263 or US-A 2011-0138504); EventMON87701 (soybean, insect control, deposited as ATCC PTA-8194, describedin US-A 2009-130071 or WO 2009/064652); Event MON87705 (soybean, qualitytrait-herbicide tolerance, deposited as ATCC PTA-9241, described in US-A2010-0080887 or WO 2010/037016); Event MON87708 (soybean, herbicidetolerance, deposited as ATCC PTA9670, described in WO 2011/034704);Event MON87754 (soybean, quality trait, deposited as ATCC PTA-9385,described in WO 2010/024976); Event MON87769 (soybean, quality trait,deposited as ATCC PTA-8911, described in US-A 2011-0067141 or WO2009/102873); Event MON88017 (corn, insect control-herbicide tolerance,deposited as ATCC PTA-5582, described in US-A 2008-028482 or WO2005/059103); Event MON88913 (cotton, herbicide tolerance, deposited asATCC PTA-4854, described in WO 2004/072235 or US-A 2006-059590); EventMON89034 (corn, insect control, deposited as ATCC PTA-7455, described inWO 2007/140256 or US-A 2008-260932); Event MON89788 (soybean, herbicidetolerance, deposited as ATCC PTA-6708, described in US-A 2006-282915 orWO 2006/130436); Event MS11 (oilseed rape, pollination control-herbicidetolerance, deposited as ATCC PTA-850 or PTA-2485, described in WO01/031042); Event MS8 (oilseed rape, pollination control-herbicidetolerance, deposited as ATCC PTA-730, described in WO 01/041558 or US-A2003-188347); Event NK603 (corn, herbicide tolerance, deposited as ATCCPTA-2478, described in US-A 2007-292854); Event PE-7 (rice, insectcontrol, not deposited, described in WO 2008/114282); Event RF3 (oilseedrape, pollination control-herbicide tolerance, deposited as ATCCPTA-730, described in WO 01/041558 or US-A 2003-188347); Event RT73(oilseed rape, herbicide tolerance, not deposited, described in WO02/036831 or US-A 2008-070260); Event T227-1 (sugar beet, herbicidetolerance, not deposited, described in WO 02/44407 or USA 2009-265817);Event T25 (corn, herbicide tolerance, not deposited, described in US-A2001-029014 or WO 01/051654); Event T304-40 (cotton, insectcontrol-herbicide tolerance, deposited as ATCC PTA-8171, described inUS-A 2010-077501 or WO 2008/122406); Event T342-142 (cotton, insectcontrol, not deposited, described in WO 2006/128568); Event TC1507(corn, insect control-herbicide tolerance, not deposited, described inUS-A 2005-039226 or WO 2004/099447); Event VIP1034 (corn, insectcontrol-herbicide tolerance, deposited as ATCC PTA-3925., described inWO 03/052073), Event 32316 (corn, insect control-herbicide tolerance,deposited as PTA-11507, described in WO 2011/084632), Event 4114(corn,insect control-herbicide tolerance, deposited as PTA-11506,described in WO 2011/084621).

Application Rates and Timing

When using the inventive active ingredients as fungicides, theapplication rates can be varied within a relatively wide range,depending on the kind of application. The application rate of theinventive active ingredients is

-   -   in the case of treatment of plant parts, for example leaves:        from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more        preferably from 10 to 800 g/ha, even more preferably from 50 to        300 g/ha (in the case of application by watering or dripping, it        is even possible to reduce the application rate, especially when        inert substrates such as rockwool or perlite are used);    -   in the case of seed treatment: from 2 to 200 g per 100 kg of        seed, preferably from 3 to 150 g per 100 kg of seed, more        preferably from 2.5 to 25 g per 100 kg of seed, even more        preferably from 2.5 to 12.5 g per 100 kg of seed;    -   in the case of soil treatment: from 0.1 to 10 000 g/ha,        preferably from 1 to 5000 g/ha.

These application rates are merely by way of example and are notlimiting for the purposes of the invention.

The inventive active ingredients or compositions can thus be used toprotect plants from attack by the pathogens mentioned for a certainperiod of time after treatment. The period for which protection isprovided extends generally for 1 to 28 days, preferably for 1 to 14days, more preferably for 1 to 10 days, most preferably for 1 to 7 days,after the treatment of the plants with the active ingredients, or for upto 200 days after a seed treatment.

The method of treatment according to the invention also provides the useor application of compounds (A) and (B) and/or (C) in a simultaneous,separate or sequential manner. If the single active ingredients areapplied in a sequential manner, i.e. at different times, they areapplied one after the other within a reasonably short period, such as afew hours or days. Preferably the order of applying the compounds (A)and (B) and/or (C) is not essential for working the present invention.

The plants listed can particularly advantageously be treated inaccordance with the invention with the compounds of the general formula(I) and the inventive compositions. The preferred ranges stated abovefor the active ingredients or compositions also apply to the treatmentof these plants. Particular emphasis is given to the treatment of plantswith the compounds or compositions specifically mentioned in the presenttext.

The invention is illustrated by the examples below. However, theinvention is not limited to the examples.

Preparation Examples

In analogy to the examples above and according to the generaldescription of the processes of preparing the compounds according to theinvention the compounds in the following Table 1 may be obtained.

TABLE 1 Ex. Hal¹ Hal² T Q X m R¹ R² R³ R⁴ R⁵ R⁶ R⁷ R⁸ logP 1 F F O H — 0H H H H H H Me Me 3.67[a] 2 F Cl O H — 0 H H H H H H Me Me 3.89[a] 3 F FO H — 0 Me H H H H H Me Me 3.92[a] 4 F Cl O H — 0 Me H H H H H Me Me4.14[a] 5 F Cl O H — 0 H H H H Me Me ═CH₂ 4.14[a] 6 F F O H — 0 H H H HMe Me ═CH₂ 3.87[a] 7 F Cl O H — 0 H H H H Me H Me H 4.09[a] R₅ and R₇are cis configurated 8 F F O H — 0 H H H H Me H Me H 3.83[a] R₅ and R₇are cis configurated 9 F F O H — 0 Me H Me H H H H H 3.68[a] R₁ and R₃are cis configurated 10 F Cl O H — 0 Me H Me H H H H H 3.92[a] R₁ and R₃are cis configurated 11 F Cl O H — 0 H H H H Me Me Me H 4.39[a] 12 F F OH — 0 H H H H Me Me Me H 4.11[a] 13 F F O H — 0 H H Me Me H H H H3.72[a] 14 F Cl O H — 0 H H Me Me H H H H 3.9[a] 15 F Cl O H — 0 H H H HMe H Me Me 4.29[a] 16 F Cl O H 4-F 1 H H H H H H Me Me 4.01[a] 17 F Cl SH 4-F 1 H H H H H H Me Me 4.24[a] 18 F F O H — 0 H H H H H H ═N—OEt3.31[a] 19 F F O H — 0 H H H H H H ═N—OMe 2.86[a] 20 F Br O H — 0 H H HH H H ═N—OEt 3.57[a] 21 F Cl O H — 0 H H H H H H ═N—OEt 3.55[a] 22 F F OH — 0 H H H H Me Me H H 3.79[a] 23 F Br O H — 0 H H H H Me Me H H4.04[a] 24 F F O H 4-F 1 H H H H H H Me Me 3.76[a] 25 F Cl O H — 0 H H HH Me Me H H 4.04[a] 26 F Br O H — 0 H H H H H H ═N—OMe 3.13[a] 27 F Cl OH — 0 Me Me H H H H H H 3.69[a] 28 F Cl O H — 0 H H H H H H ═N—OMe3.09[a] 29 F F O H — 0 Me Me H H H H H H 3.44[a] 30 F F O H — 0 H H H HH H ═N—OMe 2.86[a] 31 F Br S H — 0 H H H H Me Me H H 4.11[a] 32 F F S H— 0 H H H H Me Me H H 3.99[a] 33 F Cl S H — 0 H H H H Me Me H H 4.11[a]Me = methyl, Et = ethyl

In analogy to the examples above and according to the generaldescription of the processes of preparing the compounds according to theinvention the compounds according to formula (III-a) in the followingTable 2 may be obtained.

TABLE 2 Ex. Q X m R¹ R² R³ R⁴ R⁵ R⁶ R⁷ R⁸ logP III-a-1 H — 0 H H H H H HMe Me 1.69[a] III-a-2 H — 0 Me H H H H H Me Me 2.56[a] III-a-3 H — 0 H HH H Me Me ═CH₂ 2.44[a] III-a-4 H — 0 H H H H Me H Me H 1.93[a] R₅ and R₇cis configured III-a-5 H — 0 H H H H Me Me Me H 2.11[a] III-a-6 H — 0 HH Me Me H H H H 1.88[a] III-a-7 H — 0 H H H H Me H Me Me 2.18[a] III-a-8H 4-F 1 H H H H H H Me Me 1.96[a] III-a-9 H — 0 H H H H H H ═N—OEt1.98[a] III-a-10 H — 0 H H H H H H ═N—OMe 1.47[a] III-a-11 H — 0 Me Me HH H H H H III-a-12 H — 0 H H H H Me Me H H 1.86[a]

Measurement of log P values was performed according EEC directive 79/831Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversedphase columns with the following methods:

^([a])Measurement of LC-MS was done at pH 2.7 with 0.1% formic acid inwater and with acetonitrile (contains 0.1% formic acid) as eluent with alinear gradient from 10% acetonitrile to 95% acetonitrile.

Calibration was done with not branched alkan2-ones (with 3 to 16 carbonatoms) with known log P-values (measurement of log P values usingretention times with linear interpolation between successive alkanones).lambda-maX-values were determined using UV-spectra from 200 nm to 400 nmand the peak values of the chromatographic signals.

NMR Peak Lists

1H-NMR data of selected examples are written in form of 1H-NMR-peaklists. To each signal peak are listed the δ-value in ppm and the signalintensity in round brackets. Between the δ-value-signal intensity pairsare semicolons as delimiters.

The peak list of an example has therefore the form:

δ₁ (intensity₁); δ₂ (intensity₂); . . . ; δ_(i) (intensity_(i)); . . . ;δ_(n) (intensity_(n))

NMR Peak Lists Active Ingredient Example 1

Solvent: CDCl3, Spectrometer: 300.16 MHz

7.7063 (1.21); 7.6861 (1.34); 7.4999 (1.42); 7.2558 (1.35); 7.2212(3.52); 7.1937 (1.34); 7.0371 (1.40); 6.8578 (0.70); 3.8467 (8.14);2.6250 (2.88); 1.8477 (2.14); 1.8394 (2.16); 1.6564 (2.72); 1.6367(2.81); 1.2936 (16.00); −0.0002 (0.36)

Example 2

Solvent: CDCl3, Spectrometer: 300.16 MHz

7.7791 (1.14); 7.7239 (1.06); 7.7002 (1.13); 7.2963 (0.64); 7.2607(3.11); 7.2337 (2.78); 7.2039 (1.17); 7.1789 (0.41); 7.1160 (1.29);6.9370 (0.67); 3.9548 (7.95); 2.6702 (1.26); 2.6508 (2.51); 2.6317(1.42); 2.0456 (0.42); 1.8535 (1.62); 1.8343 (1.48); 1.6656 (2.11);1.6556 (1.78); 1.6471 (1.80); 1.5723 (1.86); 1.2980 (16.00); 1.2624(7.48); 0.8820 (3.94); 0.8593 (1.89); −0.0002 (1.41)

Example 3

Solvent: CDCl3, Spectrometer: 300.16 MHz

7.7196 (1.34); 7.7137 (1.36); 7.6954 (1.52); 7.6894 (1.54); 7.6170(1.10); 7.2721 (1.94); 7.2570 (1.39); 7.2482 (0.66); 7.2418 (1.01);7.2216 (3.45); 7.2148 (3.31); 7.2112 (3.88); 7.1867 (2.74); 7.1602(0.95); 7.0926 (4.06); 6.9131 (2.00); 3.8442 (10.51); 3.0319 (0.60);3.0280 (0.60); 3.0177 (0.64); 3.0106 (0.90); 2.9949 (0.62); 2.9876(0.65); 2.0338 (0.75); 2.0193 (0.56); 2.0097 (0.62); 2.0017 (0.55);1.9940 (0.50); 1.9756 (0.66); 1.9706 (0.71); 1.9570 (0.96); 1.9456(1.34); 1.9063 (1.00); 1.8992 (1.00); 1.8586 (0.41); 1.8521 (0.49);1.7093 (0.65); 1.6673 (0.44); 1.6596 (0.79); 1.6520 (0.85); 1.6456(0.80); 1.6247 (0.43); 1.6168 (0.66); 1.6112 (0.84); 1.6048 (0.98);1.5448 (1.28); 1.5315 (0.68); 1.5052 (0.81); 1.4957 (0.66); 1.4877(0.56); 1.3560 (16.00); 1.3060 (0.49); 1.2991 (0.50); 1.2900 (0.71);1.2669 (2.60); 1.2520 (1.36); 1.2326 (8.94); 1.2193 (15.58); 1.2093(9.49); 0.9025 (0.88); 0.8806 (3.00); 0.8574 (1.06); −0.0002 (0.78)

Example 4

Solvent: CDCl3, Spectrometer: 300.16 MHz

7.8726 (1.10); 7.6929 (1.09); 7.6867 (1.13); 7.6688 (1.25); 7.6626(1.33); 7.3405 (1.61); 7.2605 (36.02); 7.2512 (0.98); 7.2406 (3.54);7.2323 (4.84); 7.2075 (2.59); 7.1810 (0.90); 7.1606 (3.45); 6.9807(1.69); 3.9671 (15.87); 3.0668 (0.59); 3.0577 (0.61); 3.0494 (0.86);3.0348 (0.57); 3.0268 (0.64); 2.0461 (0.72); 2.0301 (0.54); 2.0209(0.57); 2.0146 (0.55); 2.0053 (0.51); 1.9866 (0.61); 1.9817 (0.66);1.9683 (0.87); 1.9550 (1.24); 1.9155 (0.96); 1.9081 (1.03); 1.8609(0.50); 1.6612 (0.45); 1.6532 (0.74); 1.6458 (0.88); 1.6398 (0.74);1.6352 (0.73); 1.6183 (0.43); 1.6106 (0.64); 1.6038 (0.80); 1.5989(0.94); 1.5473 (19.21); 1.5366 (1.04); 1.5102 (0.89); 1.5010 (0.70);1.4926 (0.59); 1.3631 (16.00); 1.3312 (0.84); 1.3061 (1.71); 1.2671(10.59); 1.2346 (11.09); 1.2265 (16.00); 1.2112 (9.78); 0.9039 (3.71);0.8820 (12.52); 0.8588 (4.53); 0.0107 (0.62); −0.0002 (25.50); −0.0111(1.13)

Example 5

Solvent: DMSO, Spectrometer: 300.16 MHz

9.5050 (1.51); 7.5404 (1.05); 7.5165 (1.24); 7.4040 (0.65); 7.3781(0.83); 7.3409 (0.94); 7.2331 (0.89); 7.2068 (1.40); 7.1806 (0.66);7.1617 (2.03); 6.9826 (0.98); 5.4994 (2.89); 5.0846 (3.06); 3.9219(7.91); 3.8659 (0.34); 3.3241 (24.45); 2.7834 (0.89); 2.7613 (1.97);2.7391 (1.02); 2.5131 (2.72); 2.5071 (5.92); 2.5011 (8.22); 2.4951(6.06); 2.4891 (2.96); 1.6431 (1.08); 1.6212 (2.41); 1.5991 (1.07);1.1006 (16.00); −0.0002 (6.13)

Example 6

Solvent: DMSO, Spectrometer: 300.16 MHz

9.3001 (1.40); 7.5376 (1.05); 7.5141 (1.20); 7.5109 (1.19); 7.4018(0.87); 7.3772 (1.15); 7.3439 (1.02); 7.2285 (0.97); 7.2023 (1.54);7.1760 (0.71); 7.1650 (2.34); 6.9861 (1.09); 5.4997 (2.87); 5.0841(3.05); 3.8302 (5.84); 3.3255 (20.12); 2.7463 (0.86); 2.7242 (1.93);2.7020 (0.98); 2.5133 (1.66); 2.5072 (3.69); 2.5011 (5.15); 2.4950(3.80); 2.4890 (1.83); 1.6364 (1.06); 1.6145 (2.40); 1.5922 (1.07);1.0997 (16.00); 1.0599 (0.49); −0.0002 (4.27)

Example 7

Solvent: DMSO, Spectrometer: 300.16 MHz

9.3525 (2.79); 7.3285 (1.92); 7.3075 (1.21); 7.2805 (1.55); 7.1645(1.38); 7.1493 (4.23); 7.1389 (3.05); 7.1132 (1.75); 7.0638 (2.73);7.0410 (1.58); 6.9701 (1.90); 3.9151 (16.00); 3.3897 (0.34); 3.3245(68.29); 3.2576 (0.34); 2.8560 (0.92); 2.8375 (1.10); 2.8317 (1.12);2.8158 (1.34); 2.7984 (0.79); 2.7593 (0.83); 2.7482 (0.99); 2.7396(1.11); 2.7290 (0.89); 2.6659 (0.61); 2.6416 (0.80); 2.6323 (0.87);2.6081 (0.95); 2.5747 (0.49); 2.5514 (0.42); 2.5129 (4.99); 2.5070(10.81); 2.5009 (15.05); 2.4948 (11.15); 2.4889 (5.49); 1.8902 (0.78);1.8755 (0.80); 1.8665 (0.72); 1.8556 (0.64); 1.6767 (0.34); 1.6669(0.41); 1.6450 (0.79); 1.6340 (1.02); 1.6203 (1.21); 1.5973 (0.89);1.5832 (0.92); 1.5601 (0.87); 1.5374 (0.54); 1.5255 (0.50); 1.0890(9.05); 1.0652 (8.97); 0.9748 (8.46); 0.9519 (8.21); 0.0106 (0.34);−0.0002 (11.04); −0.0111 (0.56)

Example 8

Solvent: DMSO, Spectrometer: 300.16 MHz

9.1512 (3.59); 7.3322 (2.67); 7.3040 (2.22); 7.2790 (2.96); 7.1610(2.33); 7.1533 (6.15); 7.1357 (4.16); 7.1103 (2.48); 7.0646 (3.52);7.0392 (2.01); 6.9743 (2.82); 5.7579 (0.88); 3.8239 (16.00); 3.3901(0.58); 3.3233 (90.95); 3.2571 (0.61); 2.8548 (1.23); 2.8389 (1.45);2.8151 (1.28); 2.7909 (0.52); 2.7603 (0.65); 2.7389 (0.64); 2.7118(1.09); 2.7010 (1.38); 2.6929 (1.41); 2.6834 (1.06); 2.6363 (0.86);2.6005 (1.14); 2.5776 (1.36); 2.5536 (0.60); 2.5435 (0.70); 2.5131(9.50); 2.5071 (20.15); 2.5010 (27.71); 2.4949 (20.28); 2.4889 (9.86);1.8919 (1.07); 1.8769 (1.07); 1.8664 (0.95); 1.8549 (0.83); 1.6627(0.54); 1.6385 (1.15); 1.6295 (1.38); 1.6159 (1.84); 1.5946 (1.34);1.5798 (1.21); 1.5594 (1.12); 1.5364 (0.69); 1.5230 (0.63); 1.0866(11.89); 1.0628 (11.79); 0.9739 (11.25); 0.9511 (10.87); 0.9099 (0.37);0.0105 (0.64); −0.0002 (23.22); −0.0111 (1.14)

Example 9

Solvent: DMSO, Spectrometer: 300.16 MHz

9.5012 (0.48); 9.2780 (1.24); 9.2587 (2.74); 8.4423 (0.40); 7.3259(2.02); 7.3213 (1.59); 7.2752 (0.74); 7.2497 (0.96); 7.2357 (1.57);7.2101 (2.35); 7.1469 (4.20); 7.1417 (2.42); 7.1335 (2.19); 7.1249(1.00); 7.1081 (3.93); 7.0995 (1.69); 7.0825 (2.34); 7.0738 (1.22);6.9910 (2.98); 6.9677 (3.99); 4.1842 (0.36); 3.9680 (2.59); 3.8318(16.00); 3.3251 (47.20); 3.0290 (1.00); 3.0145 (1.21); 3.0068 (1.10);2.9915 (1.07); 2.9691 (0.40); 2.8911 (0.38); 2.8614 (0.64); 2.8334(1.99); 2.8099 (2.61); 2.7784 (1.02); 2.7563 (0.54); 2.7249 (0.96);2.7048 (0.88); 2.5128 (6.61); 2.5070 (13.58); 2.5011 (18.32); 2.4951(13.34); 2.4894 (6.52); 1.9233 (0.34); 1.8148 (1.20); 1.7772 (0.62);1.6202 (0.58); 1.5888 (1.64); 1.5631 (2.04); 1.5342 (1.13); 1.4643(0.38); 1.4470 (0.38); 1.4226 (0.35); 1.4081 (0.34); 1.2236 (0.70);1.1151 (3.04); 1.0917 (2.95); 1.0631 (0.41); 1.0510 (0.43); 1.0377(0.41); 1.0071 (8.00); 0.9845 (7.58); 0.9257 (10.78); 0.9025 (10.63);0.8823 (1.68); 0.8590 (1.39); −0.0002 (9.77); −0.0631 (0.60)

Example 10

Solvent: DMSO, Spectrometer: 300.16 MHz

9.4694 (1.01); 9.4493 (2.06); 7.3198 (1.47); 7.3140 (0.81); 7.2239(0.57); 7.1975 (1.45); 7.1708 (1.90); 7.1400 (4.67); 7.1344 (2.08);7.1142 (2.67); 7.1049 (1.33); 7.0885 (1.40); 7.0792 (0.73); 6.9993(2.10); 6.9739 (1.52); 6.9609 (1.67); 6.9551 (0.87); 3.9669 (0.38);3.9212 (16.00); 3.3241 (62.92); 3.0711 (0.71); 3.0570 (0.77); 3.0487(0.74); 3.0329 (0.75); 2.9182 (0.39); 2.8867 (0.45); 2.8614 (0.33);2.8266 (1.10); 2.8084 (1.54); 2.7787 (0.68); 2.7583 (0.40); 2.7205(0.84); 2.7091 (0.61); 2.6581 (0.33); 2.5130 (7.43); 2.5071 (16.07);2.5010 (22.30); 2.4949 (16.50); 2.4890 (8.08); 1.8086 (0.87); 1.7730(0.44); 1.6279 (0.36); 1.5948 (1.03); 1.5714 (1.36); 1.5408 (0.75);1.4190 (0.33); 1.2198 (0.53); 1.1307 (2.62); 1.1074 (2.60); 1.0496(0.53); 1.0051 (5.62); 0.9824 (5.49); 0.9409 (5.98); 0.9180 (7.25);0.8974 (2.82); 0.0107 (0.47); −0.0002 (14.78); −0.0111 (0.70); −0.0650(0.58)

Example 11

Solvent: CDCl3, Spectrometer: 499.93 MHz

7.8325 (1.25); 7.8166 (1.40); 7.7848 (1.20); 7.2568 (12.59); 7.2379(0.84); 7.2252 (1.41); 7.2030 (1.20); 7.1874 (2.41); 7.1712 (1.85);7.1527 (0.55); 7.1172 (2.58); 7.0350 (2.25); 7.0196 (1.95); 7.0092(1.42); 3.9886 (0.33); 3.9533 (15.28); 2.6977 (0.42); 2.6933 (0.44);2.6844 (0.42); 2.6730 (0.81); 2.6640 (1.01); 2.6596 (1.01); 2.6508(0.88); 2.6268 (0.75); 2.6123 (0.97); 2.6091 (0.98); 2.5942 (1.05);2.5786 (0.48); 2.5753 (0.48); 2.5567 (0.58); 2.5417 (1.46); 2.5274(1.53); 2.5134 (0.60); 2.2687 (0.38); 1.8166 (0.56); 1.8027 (0.68);1.7984 (0.72); 1.7896 (0.84); 1.7847 (0.73); 1.7758 (0.86); 1.7715(0.91); 1.7575 (0.69); 1.6784 (1.34); 1.5358 (1.61); 1.5277 (1.31);1.5172 (1.03); 1.5139 (1.02); 1.5028 (0.92); 1.4898 (0.76); 1.4868(0.77); 1.4778 (0.66); 1.4313 (3.05); 1.2568 (1.00); 1.1871 (9.25);1.1727 (9.32); 0.9528 (15.44); 0.9387 (16.00); 0.9220 (1.31); 0.9071(0.77); 0.8957 (0.69); 0.8811 (0.46); 0.0697 (1.99); 0.0060 (0.41);−0.0002 (8.70)

Example 12

Solvent: CDCl3, Spectrometer: 499.93 MHz

7.8148 (1.24); 7.7989 (1.29); 7.5253 (0.32); 7.5097 (0.88); 7.2567(18.06); 7.2377 (0.53); 7.1961 (1.08); 7.1804 (2.27); 7.1702 (0.65);7.1647 (1.37); 7.1525 (0.43); 7.1468 (1.53); 7.0391 (3.07); 7.0283(2.05); 7.0129 (1.67); 6.9702 (0.39); 6.9313 (1.50); 3.8543 (10.08);2.6687 (0.33); 2.6641 (0.36); 2.6551 (0.33); 2.6439 (0.73); 2.6350(0.86); 2.6304 (0.88); 2.6216 (0.74); 2.6048 (0.65); 2.5906 (0.82);2.5870 (0.83); 2.5724 (0.88); 2.5523 (0.71); 2.5375 (1.51); 2.5225(1.39); 2.5086 (0.45); 2.4554 (0.36); 2.4411 (0.33); 2.2687 (0.41);1.8150 (0.62); 1.8010 (0.71); 1.7964 (0.84); 1.7880 (0.87); 1.7830(0.74); 1.7741 (0.87); 1.7700 (0.94); 1.7560 (0.72); 1.6780 (1.02);1.5434 (0.52); 1.5254 (0.73); 1.5181 (0.83); 1.5164 (0.84); 1.5133(0.88); 1.5116 (0.91); 1.5044 (0.81); 1.5025 (0.82); 1.5006 (0.79);1.4984 (0.77); 1.4913 (0.69); 1.4895 (0.69); 1.4865 (0.71); 1.4848(0.71); 1.4777 (0.59); 1.4313 (3.55); 1.2568 (0.64); 1.1844 (9.58);1.1700 (10.21); 1.1545 (1.79); 0.9508 (15.12); 0.9350 (16.00); 0.9300(4.43); 0.9219 (0.93); 0.9068 (0.42); 0.8957 (0.39); 0.0695 (4.15);0.0063 (0.40); −0.0002 (12.36); −0.0067 (0.65)

Example 13

Solvent: DMSO, Spectrometer: 300.16 MHz

9.2496 (1.23); 7.3260 (0.87); 7.2651 (0.63); 7.2401 (0.86); 7.1469(2.07); 7.1358 (0.76); 7.1103 (1.44); 7.0847 (0.86); 7.0292 (1.12);7.0065 (0.69); 6.9678 (0.99); 3.8286 (5.17); 3.3274 (40.69); 2.8133(0.72); 2.7917 (1.55); 2.7698 (0.80); 2.5134 (2.86); 2.5074 (6.42);2.5013 (9.03); 2.4952 (6.73); 2.4892 (3.29); 2.3891 (3.22); 1.5244(0.94); 1.5019 (2.04); 1.4797 (0.93); 0.9332 (16.00); −0.0002 (5.81)

Example 14

Solvent: DMSO, Spectrometer: 300.16 MHz

9.4560 (1.22); 7.3159 (0.73); 7.2555 (0.43); 7.2293 (0.60); 7.1369(2.03); 7.1133 (1.25); 7.0877 (0.74); 7.0343 (1.07); 7.0071 (0.66);6.9573 (0.80); 5.7585 (3.35); 3.9186 (6.60); 3.3250 (85.40); 3.2592(0.39); 2.8153 (0.75); 2.7934 (1.50); 2.7702 (0.86); 2.5133 (6.13);2.5073 (13.51); 2.5012 (18.89); 2.4951 (13.93); 2.4891 (6.71); 2.4249(3.23); 1.5253 (0.92); 1.5029 (2.03); 1.4807 (0.96); 0.9329 (16.00);0.0107 (0.44); −0.0002 (15.83); −0.0112 (0.69)

Example 15

Solvent: DMSO, Spectrometer: 400.13 MHz

9.3928 (2.51); 7.3481 (1.71); 7.3459 (1.77); 7.3286 (2.15); 7.3262(2.24); 7.2910 (1.44); 7.2649 (0.86); 7.2468 (1.30); 7.1995 (1.77);7.1800 (2.32); 7.1566 (3.17); 7.0221 (1.43); 5.7667 (0.51); 3.9248(14.48); 3.3919 (0.68); 3.3417 (83.14); 3.2921 (0.92); 2.7638 (0.64);2.7512 (0.40); 2.7334 (0.69); 2.7206 (1.26); 2.7079 (0.68); 2.6589(0.58); 2.6434 (0.78); 2.6357 (0.76); 2.6193 (0.79); 2.6000 (0.39);2.5923 (0.44); 2.5767 (0.36); 2.5606 (0.35); 2.5329 (0.58); 2.5281(0.94); 2.5194 (11.77); 2.5150 (24.67); 2.5105 (33.73); 2.5060 (24.21);2.5015 (11.26); 2.4652 (0.33); 2.4607 (0.41); 1.7798 (0.60); 1.7746(0.55); 1.7629 (0.71); 1.7576 (0.57); 1.7466 (0.76); 1.7305 (0.38);1.6615 (0.52); 1.6549 (0.57); 1.6446 (0.65); 1.6371 (0.98); 1.6303(0.75); 1.6197 (0.83); 1.6135 (0.71); 1.5661 (0.42); 1.5517 (0.47);1.5421 (0.65); 1.5335 (0.53); 1.5273 (0.68); 1.5186 (0.59); 1.5097(0.62); 1.5037 (0.41); 1.4948 (0.48); 1.2887 (16.00); 1.2396 (0.35);1.1348 (14.66); 0.9720 (8.71); 0.9551 (8.23); 0.9142 (0.51); 0.8991(0.54)

Example 16

Solvent: CDCl3, Spectrometer: 300.16 MHz

7.6861 (0.79); 7.6055 (0.67); 7.5893 (0.71); 7.5763 (0.77); 7.5602(0.72); 7.2616 (3.70); 7.0788 (2.46); 6.9267 (0.90); 6.8987 (1.97);6.8873 (0.99); 6.8580 (0.84); 3.9522 (11.61); 2.6404 (1.28); 2.6199(2.71); 2.5988 (1.61); 1.8284 (0.39); 1.8189 (0.41); 1.8079 (0.97);1.7975 (0.96); 1.7899 (1.27); 1.7760 (1.06); 1.7695 (1.44); 1.7551(0.53); 1.7492 (0.59); 1.6599 (2.07); 1.6536 (1.48); 1.6412 (1.24);1.6316 (1.13); 1.6222 (1.24); 1.5824 (1.22); 1.3832 (16.00); 1.3777(16.00); −0.0002 (3.06)

Example 17

Solvent: CDCl3, Spectrometer: 300.16 MHz

8.6484 (0.51); 7.2995 (0.58); 7.2835 (0.62); 7.2703 (0.80); 7.2621(4.19); 7.2551 (0.76); 7.1862 (0.74); 7.0060 (1.52); 6.9668 (0.62);6.9379 (0.59); 6.9278 (0.67); 6.8990 (0.52); 6.8259 (0.76); 4.1543(1.16); 4.1304 (3.49); 4.1066 (3.55); 4.0829 (1.21); 3.9237 (6.82);2.6811 (0.78); 2.6608 (1.62); 2.6397 (1.01); 2.1682 (1.81); 2.0423(16.00); 1.7823 (0.66); 1.7652 (0.91); 1.7497 (0.90); 1.7314 (0.53);1.7236 (0.38); 1.6796 (0.42); 1.6688 (1.33); 1.6632 (1.30); 1.6498(0.96); 1.6420 (0.92); 1.6321 (0.86); 1.5763 (1.45); 1.4003 (9.53);1.3951 (9.60); 1.3561 (0.73); 1.3304 (0.56); 1.3067 (1.10); 1.2817(6.06); 1.2664 (6.94); 1.2580 (13.11); 1.2341 (4.73); 0.9036 (2.42);0.8818 (7.87); 0.8585 (2.96); −0.0002 (3.45)

Example 18

Solvent: DMSO, Spectrometer: 400.13 MHz

9.5352 (3.08); 7.8126 (2.18); 7.8097 (2.32); 7.7928 (2.44); 7.7899(2.40); 7.4060 (1.79); 7.3890 (2.24); 7.3866 (2.14); 7.2784 (1.72);7.2493 (2.05); 7.2296 (3.48); 7.2099 (1.57); 7.1441 (4.10); 7.0099(1.92); 5.7529 (5.93); 4.2032 (2.01); 4.1857 (6.55); 4.1681 (6.67);4.1505 (2.09); 3.8308 (11.79); 3.3071 (53.36); 2.6731 (2.21); 2.6568(3.84); 2.6402 (2.33); 2.6191 (1.90); 2.6042 (3.12); 2.5888 (2.04);2.5089 (7.55); 2.5045 (15.70); 2.4999 (21.40); 2.4954 (15.04); 2.4910(6.95); 1.9875 (0.45); 1.7539 (0.60); 1.7376 (1.79); 1.7217 (2.42);1.7070 (1.71); 1.6905 (0.52); 1.4363 (0.47); 1.3554 (0.49); 1.2845(7.35); 1.2670 (16.00); 1.2494 (7.23); 0.0080 (0.61); −0.0002 (20.10);−0.0085 (0.67)

Example 19

Solvent: DMSO, Spectrometer: 400.13 MHz

9.5370 (2.03); 7.8019 (1.38); 7.7994 (1.43); 7.7822 (1.52); 7.7796(1.48); 7.4148 (1.13); 7.3966 (1.42); 7.2773 (1.09); 7.2536 (1.25);7.2339 (2.11); 7.2142 (0.96); 7.1430 (2.54); 7.0089 (1.23); 5.7527(0.77); 3.9190 (16.00); 3.8307 (7.66); 3.7662 (0.62); 3.3076 (53.74);2.6696 (1.50); 2.6533 (2.56); 2.6367 (1.56); 2.6196 (1.29); 2.6048(2.09); 2.5892 (1.35); 2.5090 (5.78); 2.5045 (11.55); 2.5000 (15.40);2.4955 (10.78); 2.4911 (5.02); 1.7527 (0.40); 1.7364 (1.19); 1.7209(1.64); 1.7058 (1.12); 1.6896 (0.36); 0.0079 (0.43); −0.0002 (11.18);−0.0085 (0.43)

Example 20

Solvent: DMSO, Spectrometer: 300.16 MHz

9.7782 (0.74); 7.8164 (0.41); 7.8127 (0.42); 7.7900 (0.46); 7.7863(0.45); 7.3783 (0.32); 7.3092 (0.33); 7.2609 (0.35); 7.2346 (0.58);7.1299 (0.73); 6.9507 (0.35); 5.7577 (2.11); 4.2130 (0.37); 4.1897(1.16); 4.1663 (1.19); 4.1429 (0.38); 3.9431 (2.76); 3.3221 (16.00);2.6827 (0.68); 2.6618 (1.16); 2.6459 (0.61); 2.5128 (1.90); 2.5070(3.96); 2.5009 (5.41); 2.4949 (3.98); 2.4890 (1.94); 1.7527 (0.35);1.7314 (0.45); 1.7122 (0.34); 1.2908 (1.28); 1.2674 (2.78); 1.2440(1.28); −0.0002 (3.96)

Example 21

Solvent: DMSO, Spectrometer: 400.13 MHz

9.7283 (3.31); 7.8157 (2.06); 7.8128 (2.20); 7.7959 (2.29); 7.7931(2.28); 7.4117 (1.12); 7.3925 (1.33); 7.2763 (1.59); 7.2545 (1.72);7.2348 (2.92); 7.2152 (1.31); 7.1419 (3.68); 7.0076 (1.76); 4.2040(2.00); 4.1864 (6.52); 4.1689 (6.61); 4.1513 (2.10); 3.9217 (14.31);3.3068 (72.09); 2.6752 (2.20); 2.6592 (5.38); 2.6432 (4.72); 2.6300(2.06); 2.5090 (10.43); 2.5045 (21.67); 2.4999 (29.48); 2.4954 (20.60);2.4909 (9.42); 1.9876 (0.48); 1.7636 (0.60); 1.7475 (1.75); 1.7319(2.26); 1.7167 (1.65); 1.6999 (0.52); 1.2850 (7.33); 1.2674 (16.00);1.2498 (7.20); 0.0080 (1.05); −0.0002 (34.09); −0.0085 (1.11)

Example 22

Solvent: DMSO, Spectrometer: 400.13 MHz

9.1938 (1.15); 7.3253 (0.67); 7.3056 (0.88); 7.3001 (1.05); 7.1657(1.78); 7.1362 (0.71); 7.1169 (1.33); 7.0976 (0.72); 7.0315 (0.85);6.9592 (1.00); 6.9417 (0.81); 3.8324 (5.39); 3.3155 (2.87); 2.6742(0.80); 2.6574 (1.58); 2.6406 (0.84); 2.5378 (3.21); 2.5255 (0.88);2.5166 (5.39); 2.5121 (10.70); 2.5076 (14.45); 2.5030 (10.39); 2.4985(5.20); 1.5480 (0.92); 1.5312 (1.92); 1.5142 (0.90); 0.9493 (16.00)

Example 23

Solvent: DMSO, Spectrometer: 300.16 MHz

9.4357 (1.37); 7.3181 (0.92); 7.3104 (0.60); 7.2828 (0.66); 7.1387(2.26); 7.1123 (1.26); 7.0866 (0.67); 6.9589 (1.63); 6.9312 (0.81);3.9384 (7.28); 3.3232 (10.60); 2.7310 (0.75); 2.7086 (1.57); 2.6867(0.82); 2.5325 (3.09); 2.5128 (1.68); 2.5068 (3.42); 2.5007 (4.75);2.4946 (3.54); 2.4886 (1.74); 1.9886 (0.36); 1.5493 (0.89); 1.5271(1.91); 1.5046 (0.88); 1.3551 (0.80); 0.9425 (16.00); 0.9097 (0.41);−0.0002 (3.54)

Example 24

Solvent: CDCl3, Spectrometer: 300.16 MHz

7.5852 (0.77); 7.5690 (0.83); 7.5560 (0.90); 7.5399 (0.87); 7.4107(0.80); 7.2627 (1.87); 7.1766 (1.25); 6.9972 (2.56); 6.9164 (0.95);6.8870 (0.96); 6.8769 (1.02); 6.8476 (0.89); 6.8178 (1.30); 3.8496(8.16); 2.6161 (1.39); 2.5956 (2.92); 2.5746 (1.71); 2.0426 (0.57);1.8249 (0.42); 1.8151 (0.44); 1.8043 (1.03); 1.7937 (1.07); 1.7862(1.40); 1.7723 (1.15); 1.7660 (1.53); 1.7513 (0.57); 1.7458 (0.63);1.6564 (2.21); 1.6504 (1.61); 1.6375 (1.38); 1.6283 (1.24); 1.6186(1.38); 1.6126 (1.02); 1.3788 (16.00); 1.3735 (15.75); 1.2577 (0.42);−0.0002 (1.64)

Example 25

Solvent: DMSO, Spectrometer: 400.13 MHz

9.3964 (1.09); 7.3238 (0.43); 7.3047 (0.53); 7.2953 (0.83); 7.1608(1.48); 7.1394 (0.63); 7.1201 (1.17); 7.1008 (0.61); 7.0263 (0.71);6.9623 (1.00); 6.9441 (0.79); 3.9242 (6.91); 3.3150 (2.95); 2.7113(0.75); 2.6947 (1.58); 2.6775 (0.85); 2.5397 (3.12); 2.5164 (5.57);2.5119 (11.07); 2.5074 (14.84); 2.5029 (10.37); 2.4985 (4.78); 1.5529(0.92); 1.5360 (1.92); 1.5190 (0.85); 0.9499 (16.00)

Example 26

Solvent: DMSO, Spectrometer: 300.16 MHz

9.7855 (2.57); 7.8028 (1.53); 7.7796 (1.69); 7.4121 (0.91); 7.3873(1.20); 7.3096 (1.18); 7.2655 (1.28); 7.2393 (2.02); 7.2129 (0.90);7.1303 (2.58); 6.9510 (1.23); 5.7585 (0.56); 3.9431 (10.41); 3.9203(16.00); 3.8877 (0.50); 3.8614 (0.42); 3.3257 (14.74); 2.6786 (2.49);2.6577 (3.83); 2.6354 (2.00); 2.5069 (5.03); 2.5010 (6.73); 2.4950(4.99); 1.7717 (0.47); 1.7508 (1.35); 1.7305 (1.75); 1.7104 (1.26);−0.0002 (4.30)

Example 27

Solvent: DMSO, Spectrometer: 400.13 MHz

9.4020 (1.32); 7.2991 (0.74); 7.1643 (1.70); 7.1420 (0.61); 7.1230(1.60); 7.1041 (1.13); 7.0469 (0.94); 7.0295 (1.39); 6.9288 (0.84);6.9116 (0.71); 3.9279 (6.81); 3.3148 (6.79); 2.7954 (0.62); 2.7805(1.31); 2.7649 (0.74); 2.5164 (7.58); 2.5120 (15.54); 2.5075 (21.04);2.5031 (14.95); 2.4987 (7.03); 1.7202 (0.48); 1.7076 (0.71); 1.6936(0.76); 1.6776 (0.35); 1.6276 (1.05); 1.6144 (0.72); 1.6087 (0.73);1.6012 (0.59); 1.3560 (16.00)

Example 28

Solvent: DMSO, Spectrometer: 400.13 MHz

9.7338 (2.04); 7.8062 (1.45); 7.7878 (1.49); 7.4237 (0.89); 7.4030(1.06); 7.2759 (0.75); 7.2599 (0.89); 7.2401 (1.41); 7.2234 (0.64);7.1414 (1.44); 7.0116 (0.67); 7.0075 (0.71); 5.7585 (2.55); 5.7548(2.46); 5.7528 (3.56); 3.9242 (15.99); 3.9220 (16.00); 3.3120 (28.91);3.3065 (39.73); 3.2629 (0.33); 2.6578 (3.59); 2.6455 (3.26); 2.5047(25.16); 2.5004 (25.09); 1.9932 (0.47); 1.9876 (0.58); 1.7482 (1.31);1.7337 (1.77); 1.7185 (1.30); 1.1745 (0.39); 0.0055 (8.29); 0.0019(8.42); −0.0002 (12.67)

Example 29

Solvent: DMSO, Spectrometer: 400.13 MHz

9.2638 (1.29); 7.2998 (0.70); 7.1653 (1.67); 7.1335 (0.64); 7.1145(1.68); 7.0956 (1.22); 7.0398 (0.99); 7.0310 (0.90); 7.0240 (0.62);6.9557 (0.85); 6.9532 (0.84); 6.9368 (0.70); 3.8430 (4.98); 3.3147(6.37); 2.7919 (0.62); 2.7769 (1.31); 2.7613 (0.73); 2.5297 (0.41);2.5164 (7.83); 2.5120 (15.68); 2.5074 (21.03); 2.5029 (14.75); 2.4985(6.82); 1.7177 (0.49); 1.7051 (0.72); 1.6919 (0.76); 1.6778 (0.41);1.6278 (1.06); 1.6149 (0.74); 1.6092 (0.73); 1.6020 (0.58); 1.3281(16.00)

Example 30

Solvent: DMSO, Spectrometer: 400.13 MHz

9.5370 (1.87); 7.8020 (1.26); 7.7993 (1.34); 7.7821 (1.41); 7.7794(1.39); 7.4147 (1.04); 7.3968 (1.30); 7.2773 (1.04); 7.2535 (1.19);7.2338 (2.02); 7.2142 (0.92); 7.1431 (2.49); 7.0089 (1.17); 5.7529(0.79); 3.9190 (16.00); 3.8306 (7.02); 3.3073 (36.81); 2.6695 (1.34);2.6534 (2.31); 2.6366 (1.43); 2.6196 (1.16); 2.6046 (1.89); 2.5894(1.21); 2.5090 (4.46); 2.5045 (9.21); 2.4999 (12.55); 2.4954 (8.74);2.4910 (3.99); 1.9876 (0.38); 1.7528 (0.37); 1.7366 (1.08); 1.7211(1.44); 1.7058 (1.01); 0.0080 (0.32); −0.0002 (9.86); −0.0085 (0.33)

Example 31

Solvent: CDCl3, Spectrometer: 300.16 MHz

8.6933 (0.38); 7.3641 (0.48); 7.3385 (0.72); 7.2605 (12.90); 7.2391(0.47); 7.2129 (0.80); 7.1873 (0.42); 7.1070 (0.68); 7.0811 (0.46);7.0252 (0.86); 6.8451 (0.43); 3.9686 (4.29); 3.7046 (16.00); 2.7746(0.64); 2.7522 (1.27); 2.7296 (0.70); 2.5989 (2.14); 1.6122 (0.75);1.5901 (1.40); 1.5676 (0.71); 1.5450 (4.38); 1.4323 (0.50); 1.2553(1.02); 0.9878 (15.69); 0.0694 (0.39); 0.0106 (0.37); −0.0002 (11.89);−0.0111 (0.63)

Example 32

Solvent: CDCl3, Spectrometer: 300.16 MHz

7.2769 (0.56); 7.2727 (0.55); 7.2605 (22.22); 7.2279 (0.35); 7.2029(0.45); 7.1612 (0.56); 7.1009 (0.46); 7.0763 (0.34); 6.9816 (1.01);6.8019 (0.52); 3.8362 (2.13); 3.7053 (3.56); 2.7405 (0.63); 2.7184(1.36); 2.6959 (0.75); 2.5925 (2.17); 1.5986 (0.62); 1.5765 (1.16);1.5531 (0.67); 1.5413 (5.94); 0.9828 (16.00); 0.0106 (0.58); −0.0002(19.90); −0.0111 (0.85)

Example 33

Solvent: CDCl3, Spectrometer: 300.16 MHz

7.2608 (6.69); 7.2118 (0.36); 7.0441 (0.38); 3.9306 (1.92); 3.7046(16.00); 2.7411 (0.62); 2.7193 (0.33); 2.5981 (1.00); 1.6091 (0.35);1.5867 (0.63); 1.5643 (0.32); 1.5492 (2.77); 0.9867 (8.58); −0.0002(6.07)

NMR Peak Lists Intermediates Example III-a-1

Solvent: DMSO, Spectrometer: 400.13 MHz

7.4072 (0.71); 7.4044 (0.74); 7.3882 (0.84); 7.3855 (0.85); 7.2403(0.49); 7.2210 (1.27); 7.2019 (1.03); 7.1904 (1.29); 7.1868 (1.35);7.1711 (0.54); 7.1676 (0.44); 2.7062 (0.88); 2.6903 (1.83); 2.6744(1.04); 2.5162 (9.57); 2.5118 (19.10); 2.5074 (25.59); 2.5029 (18.14);2.4986 (8.56); 1.7854 (0.67); 1.7776 (0.69); 1.7710 (0.90); 1.7619(0.73); 1.7558 (0.85); 1.7400 (0.32); 1.6198 (1.30); 1.6137 (0.99);1.6048 (1.00); 1.5984 (0.87); 1.5907 (0.89); 1.2545 (16.00)

Example III-a-2

Solvent: CDCl3, Spectrometer: 300.16 MHz

7.3040 (4.46); 7.0623 (1.18); 7.0363 (2.78); 7.0104 (1.76); 6.8797(1.99); 6.8773 (1.97); 6.8537 (1.52); 6.5699 (2.00); 6.5664 (1.82);6.5443 (1.81); 6.5408 (1.63); 5.3452 (2.27); 3.6752 (0.91); 2.9112(0.60); 2.8890 (0.90); 2.8728 (0.59); 2.8662 (0.63); 2.0669 (0.65);2.0584 (0.73); 2.0496 (0.66); 2.0414 (0.52); 2.0243 (0.64); 2.0182(0.70); 2.0037 (0.84); 1.9888 (1.24); 1.9491 (0.99); 1.9413 (1.01);1.9016 (0.42); 1.8943 (0.52); 1.6840 (0.59); 1.6762 (0.90); 1.6685(0.96); 1.6612 (0.99); 1.6561 (0.73); 1.6412 (0.56); 1.6338 (0.79);1.6276 (0.95); 1.6213 (1.10); 1.5558 (1.23); 1.5416 (0.73); 1.5145(0.85); 1.5061 (0.71); 1.4980 (0.61); 1.3789 (16.00); 1.3362 (0.38);1.3234 (0.49); 1.2960 (9.12); 1.2724 (10.77); 1.2647 (15.36); 0.0499(2.65)

Example III-a-3

Solvent: DMSO, Spectrometer: 400.13 MHz

6.8851 (0.43); 6.8657 (1.12); 6.8464 (0.85); 6.8110 (0.93); 6.8085(1.00); 6.7916 (0.56); 6.7890 (0.52); 6.5491 (0.86); 6.5462 (0.85);6.5301 (0.77); 6.5271 (0.74); 5.3316 (1.96); 4.9414 (1.99); 4.9403(1.98); 4.7940 (1.46); 4.0372 (0.39); 4.0195 (0.39); 3.3304 (5.99);2.5104 (0.61); 2.5059 (1.28); 2.5014 (1.74); 2.4969 (1.23); 2.4925(0.58); 2.4539 (0.71); 2.4372 (1.50); 2.4205 (0.77); 1.9889 (1.75);1.6380 (1.14); 1.6213 (2.41); 1.6044 (1.12); 1.4487 (0.57); 1.2518(0.39); 1.2345 (0.41); 1.1919 (0.58); 1.1741 (1.09); 1.1563 (0.59);1.0771 (0.57); 1.0734 (0.82); 1.0643 (16.00); −0.0002 (1.91)

Example III-a-4

Solvent: DMSO, Spectrometer: 400.13 MHz

6.8079 (1.90); 6.7887 (4.05); 6.7695 (2.41); 6.4182 (2.99); 6.4154(3.70); 6.3987 (2.94); 6.3959 (3.33); 6.3514 (3.12); 6.3331 (2.94);4.6584 (0.96); 3.3307 (8.71); 2.6991 (0.34); 2.6816 (1.17); 2.6695(1.33); 2.6642 (1.39); 2.6521 (1.29); 2.6345 (0.47); 2.5095 (1.25);2.5050 (2.77); 2.5004 (3.95); 2.4959 (2.97); 2.4915 (1.53); 2.4594(1.07); 2.4525 (0.82); 2.4441 (0.87); 2.4363 (0.78); 2.4171 (1.15);2.4093 (1.29); 2.4007 (1.80); 2.3934 (1.25); 2.3154 (0.89); 2.2974(1.07); 2.2903 (1.16); 2.2722 (1.53); 2.2544 (0.66); 2.2473 (0.75);2.2292 (0.64); 1.8596 (0.44); 1.8514 (0.56); 1.8485 (0.64); 1.8404(0.80); 1.8317 (1.09); 1.8233 (1.09); 1.8207 (0.99); 1.8145 (0.99);1.8065 (0.85); 1.8034 (0.83); 1.7952 (0.67); 1.6553 (0.52); 1.6473(0.57); 1.6371 (0.66); 1.6306 (1.06); 1.6225 (1.34); 1.6142 (1.33);1.6036 (1.77); 1.5866 (1.01); 1.5769 (1.25); 1.5702 (0.68); 1.5593(1.18); 1.5537 (0.73); 1.5496 (0.90); 1.5444 (0.72); 1.5332 (0.76);1.5279 (0.63); 1.5167 (0.44); 1.5003 (0.34); 1.0254 (15.93); 1.0076(16.00); 0.9759 (0.33); 0.9625 (0.35); 0.9470 (14.42); 0.9298 (14.16);0.9099 (0.74); −0.0002 (5.12)

Example III-a-5

Solvent: CDCl3, Spectrometer: 499.93 MHz

7.2423 (2.07); 6.9830 (0.98); 6.9676 (2.08); 6.9522 (1.13); 6.6258(1.74); 6.6105 (1.59); 6.5127 (1.63); 6.4973 (1.52); 3.5341 (1.46);2.4917 (0.36); 2.4833 (0.65); 2.4688 (1.47); 2.4593 (1.00); 2.4529(1.68); 2.4457 (1.02); 2.4372 (1.68); 2.4225 (0.90); 2.4198 (0.89);2.4050 (0.84); 1.8123 (0.56); 1.7980 (0.64); 1.7945 (0.65); 1.7855(0.73); 1.7802 (0.60); 1.7710 (0.77); 1.7679 (0.79); 1.7534 (0.64);1.5463 (2.05); 1.5177 (0.54); 1.5161 (0.54); 1.5067 (0.63); 1.5043(0.65); 1.5025 (0.59); 1.4948 (0.58); 1.4926 (0.67); 1.4797 (0.55);1.4777 (0.55); 1.4758 (0.49); 1.4682 (0.43); 1.4666 (0.42); 1.1673(9.95); 1.1530 (9.84); 0.9358 (16.00); 0.9279 (15.46); −0.0002 (1.44)

Example III-a-6

Solvent: DMSO, Spectrometer: 300.16 MHz

6.7886 (0.56); 6.7631 (1.23); 6.7377 (0.75); 6.4262 (1.05); 6.4005(0.92); 6.3289 (0.91); 6.3038 (0.85); 4.6381 (1.70); 3.3301 (2.47);2.6667 (0.96); 2.6448 (1.90); 2.6232 (1.09); 2.4992 (0.67); 2.4940(0.53); 2.1355 (3.03); 1.4655 (1.20); 1.4434 (2.33); 1.4213 (1.15);1.2321 (0.37); 1.0651 (0.52); 1.0443 (0.53); 0.9547 (16.00); −0.0002(0.38)

Example III-a-8

Solvent: DMSO, Spectrometer: 400.13 MHz

6.6674 (0.87); 6.6460 (1.08); 6.6362 (0.93); 6.6147 (1.04); 6.4678(1.46); 6.4562 (1.54); 6.4463 (1.26); 6.4347 (1.20); 4.5397 (2.95);3.3237 (1.38); 2.5160 (1.32); 2.5118 (2.53); 2.5073 (3.35); 2.5030(2.43); 2.3359 (1.54); 2.3202 (3.07); 2.3044 (1.69); 1.7242 (0.46);1.7171 (0.46); 1.7086 (1.16); 1.7010 (1.10); 1.6946 (1.52); 1.6852(1.13); 1.6794 (1.48); 1.6691 (0.50); 1.6636 (0.60); 1.5678 (2.25);1.5623 (1.55); 1.5529 (1.55); 1.5461 (1.32); 1.5389 (1.47); 1.2905(15.90); 1.2869 (16.00)

Example III-a-9

Solvent: DMSO, Spectrometer: 300.16 MHz

7.1435 (1.97); 7.1398 (2.05); 7.1174 (2.52); 7.1136 (2.40); 6.8988(1.62); 6.8727 (3.21); 6.8466 (1.67); 6.6232 (2.69); 6.6191 (2.79);6.5971 (2.37); 6.5931 (2.22); 4.9078 (4.76); 4.1534 (2.14); 4.1300(6.97); 4.1065 (7.11); 4.0831 (2.29); 3.3251 (19.52); 2.6184 (2.30);2.5975 (3.65); 2.5743 (2.71); 2.5130 (1.59); 2.5070 (3.41); 2.5009(4.70); 2.4948 (3.44); 2.4887 (1.67); 2.4483 (1.94); 2.4279 (3.62);2.4073 (2.22); 1.7683 (0.65); 1.7465 (1.88); 1.7256 (2.51); 1.7046(1.76); 1.6829 (0.59); 1.2606 (7.36); 1.2372 (16.00); 1.2137 (7.18);−0.0002 (3.03)

Example III-a-10

Solvent: DMSO, Spectrometer: 300.16 MHz

7.1333 (1.07); 7.1296 (1.11); 7.1071 (1.37); 7.1034 (1.32); 6.9027(0.88); 6.8766 (1.73); 6.8505 (0.91); 6.6299 (1.46); 6.6259 (1.50);6.6039 (1.28); 6.5998 (1.21); 4.9164 (2.59); 3.8618 (16.00); 3.3272(6.95); 2.6134 (1.30); 2.5924 (2.06); 2.5693 (1.55); 2.5127 (0.50);2.5067 (1.04); 2.5006 (1.43); 2.4945 (1.06); 2.4886 (0.52); 2.4481(1.09); 2.4276 (2.02); 2.4070 (1.26); 1.7672 (0.37); 1.7453 (1.07);1.7244 (1.43); 1.7033 (1.00); 1.6819 (0.33); −0.0002 (0.74)

Intensity of sharp signals correlates with the height of the signals ina printed example of a NMR spectrum in cm and shows the real relationsof signal intensities. From broad signals several peaks or the middle ofthe signal and their relative intensity in comparison to the mostintensive signal in the spectrum can be shown.

For calibrating chemical shift for 1H spectra, we use tetramethylsilaneand/or the chemical shift of the solvent used, especially in the case ofspectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilanepeak can occur but not necessarily.

The 1H-NMR peak lists are similar to classical 1H-NMR prints and containtherefore usually all peaks, which are listed at classicalNMR-interpretation.

Additionally they can show like classical 1H-NMR prints signals ofsolvents, stereoisomers of the target compounds, which are also objectof the invention, and/or peaks of impurities.

To show compound signals in the delta-range of solvents and/or water theusual peaks of solvents, for example peaks of DMSO in DMSO-D₆ and thepeak of water are shown in our 1H-NMR peak lists and have usually onaverage a high intensity.

The peaks of stereoisomers of the target compounds and/or peaks ofimpurities have usually on average a lower intensity than the peaks oftarget compounds (for example with a purity>90%).

Such stereoisomers and/or impurities can be typical for the specificpreparation process. Therefore their peaks can help to recognize thereproduction of our preparation process via“side-products-fingerprints”.

An expert, who calculates the peaks of the target compounds with knownmethods (MestreC, ACD-simulation, but also with empirically evaluatedexpectation values) can isolate the peaks of the target compounds asneeded optionally using additional intensity filters. This isolationwould be similar to relevant peak picking at classical 1H-NMRinterpretation.

Further details of NMR-data description with peak lists you find in thepublication “Citation of NMR Peaklist Data within Patent Applications”of the Research Disclosure Database Number 564025.

Example In Vivo Preventive Test on Alternaria brassicae (Leaf Spot onRadish)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Radish plants (“Pernod Clair” variety), sown in starter cups on a 50/50peat soil-pozzolana substrate and grown at 17° C., are treated at thecotyledon stage by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the cotyledonswith an aqueous suspension of Alternaria brassicae spores (50 000 sporesper ml). The spores are collected from a 15-day-old culture. Thecontaminated radish plants are incubated at 20° C. and at 100% relativehumidity.

Grading (% of efficacy) is carried out 6 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 500 ppm with the following compounds:

Ex_no. Eff. % 1 93 3 93 4 92 6 97 7 97 8 97 14 71 18 83 19 96 22 80 2475 25 70 30 96

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 100 ppm with the following compounds:

Ex_no. Eff. % 32 75 33 75

Example In Vivo Preventive Test on Botrytis cinerea (Grey Mould)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO and then diluted with water to obtain thedesired active material concentration.

Gherkin plants (“Vert petit de Paris” variety), sown in starter cups ona 50/50 peat soil-pozzolana substrate and grown at 24° C., are treatedat the Z11 cotyledon stage by spraying with the active ingredientprepared as described above. Plants, used as controls, are treated withthe mixture of acetone/tween/DMSO/water not containing the activematerial.

After 24 hours, the plants are contaminated by spraying the cotyledonswith an aqueous suspension of cryopreserved Botrytis cinerea spores (50000 spores per ml). The spores are suspended in a nutrient solutioncomposed of 10 g/L of PDB, 50 g/L of D-Fructose, 2 g/L of NH₄NO₃ and 1g/L of KH₂PO₄. The contaminated gherkin plants are incubated at 17° C.and at 90% relative humidity.

Grading (% of efficacy) is carried out 4 to 5 days after thecontamination, in comparison with the control plants.

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 500 ppm with the following compounds:

Ex_no. Eff. % 3 100 5 93 6 97 19 96 22 99 25 97 30 96

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 100 ppm with the following compounds:

Ex_no. Eff. % 32 73

Example In Vivo Preventive Test on Pyrenophora teres (Net Blotch onBarley)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Barley plants (“Plaisant” variety), sown in starter cups on a 50/50 peatsoil-pozzolana substrate and grown at 22° C., are treated at the 1-leafstage (10 cm height) by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Pyrenophora teres spores (12 000 spores perml). The spores are collected from a 12-day-old culture. Thecontaminated barley plants are incubated for 48 hours at 20° C. and at100% relative humidity, and then for 12 days at 20° C. at 70-80%relative humidity.

Grading (% of efficacy) is carried out 14 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 500 ppm with the following compounds:

Ex_no. Eff. % 6 80 8 71 9 86 10 86 12 81 13 75 14 97 18 92 21 75 22 70

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 100 ppm with the following compounds:

Ex_no. Eff. % 32 83

Example In Vivo Preventive Test on Pyricularia oryzae (Rice Blast)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Rice plants (“Koshihikari” variety), sown in starter cups on a 50/50peat soil-pozzolana substrate and grown at 26° C., are treated at the2-leaf stage (10 cm height) by spraying with the active ingredientprepared as described above. Plants, used as controls, are treated withthe mixture of acetone/tween/DMSO/water not containing the activematerial.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Pyricularia oryzae spores (40 000 spores perml). The spores are collected from a 15-day-old culture and aresuspended in water containing 2.5 g/1 of gelatin. The contaminated riceplants are incubated at 25° C. and at 80% relative humidity.

Grading (% of efficacy) is carried out 6 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 500 ppm with the following compounds:

Ex_no. Eff. % 12 71

Example In Vivo Preventive Test on Puccinia recondita (Brown Rust onWheat)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Wheat plants (“Scipion” variety), sown in starter cups on a 50/50 peatsoil-pozzolana substrate and grown at 22° C., are treated at the 1-leafstage (10 cm height) by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Puccinia recondita spores (100 000 spores perml). The spores are collected from an infected plant and are suspendedin water containing 2.5 ml/l of Tween 80 at 10%. The contaminated wheatplants are incubated for 24 hours at 20° C. and at 100% relativehumidity, and then for 10 days at 20° C. and at 70-80% relativehumidity.

Grading (% of efficacy) is carried out 12 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 500 ppm with the following compounds:

Ex_no. Eff. % 1 100 2 98 3 94 4 94 5 94 6 89 7 100 8 100 9 94 10 94 1198 12 100 13 97 14 100 15 98 16 97 17 100 21 94 22 94 23 79 24 97 25 98

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 100 ppm with the following compounds:

Ex_no. Eff. % 32 94 33 94

Example In Vivo Preventive Test on Septoria tritici (Leaf Spot on Wheat)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Wheat plants (“Scipion” variety), sown in starter cups on a 50/50 peatsoil-pozzolana substrate and grown at 22° C., are treated at the 1-leafstage (10 cm height) by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of cryopreserved Septoria tritici spores (500 000spores per ml). The contaminated wheat plants are incubated for 72 hoursat 18° C. and at 100% relative humidity, and then for 21 days at 90%relative humidity.

Grading (% of efficacy) is carried out 24 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 500 ppm with the following compounds:

Ex_no. Eff. % 1 88 6 75 9 83 10 83 13 95 14 90 15 75 22 83 25 100

Example In Vivo Preventive Test on Sphaerotheca fuliginea (PowderyMildew on Cucurbits)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO and then diluted with water to obtain thedesired active material concentration.

Gherkin plants (“Vert petit de Paris” variety), sown in starter cups ona 50/50 peat soil-pozzolana substrate and grown at 24° C., are treatedat the Z11 cotyledon stage by spraying with the active ingredientprepared as described above. Plants, used as controls, are treated withthe mixture of acetone/tween/DMSO/water not containing the activematerial.

After 24 hours, the plants are contaminated by spraying the cotyledonswith an aqueous suspension of Sphaerotheca fuliginea spores (100 000spores per ml). The spores are collected from infected plants. Thecontaminated gherkin plants are incubated at about 20° C. and at 70-80%relative humidity.

Grading (% of efficacy) is carried out 12 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 500 ppm with the following compounds:

Ex_no. Eff. % 6 70 8 85 9 100 10 89 12 100 13 98 14 98 15 70 22 100

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 100 ppm with the following compounds:

Ex_no. Eff. % 32 98

Example In Vivo Preventive Test on Uromyces appendiculatus (Bean Rust)

The active ingredients tested are prepared by homogenization in amixture of acetone/tween/DMSO, and then diluted with water to obtain thedesired active material concentration.

Bean plants (“Saxa” variety), sown in starter cups on a 50/50 peatsoil-pozzolana substrate and grown at 24° C., are treated at the 2-leafstage (9 cm height) by spraying with the active ingredient prepared asdescribed above. Plants, used as controls, are treated with the mixtureof acetone/tween/DMSO/water not containing the active material.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Uromyces appendiculatus spores (150 000 sporesper ml). The spores are collected from infected plants and are suspendedin water containing 2.5 ml/l of Tween 80 at 10%. The contaminated beanplants are incubated for 24 hours at 20° C. and at 100% relativehumidity, and then for 10 days at 20° C. and at 70-80% relativehumidity.

Grading (% of efficacy) is carried out 11 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 500 ppm with the following compounds:

Ex_no. Eff. % 1 100 2 100 3 100 4 99 5 100 6 97 7 100 8 99 9 100 10 9911 100 12 100 13 100 14 99 15 95 16 100 17 100 18 81 22 100 23 96 24 10025 100

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 100 ppm with the following compounds:

Ex_no. Eff. % 32 97 33 99

Example In Vivo Phakopsora Test (Soybeans)/Preventive

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier:   1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous spore suspension of the causal agent of soybean rust (Phakopsorapachyrhizi) and stay for 24 h without light in an incubation cabinet atapproximately 24° C. and a relative atmospheric humidity of 95%.

The plants remain in the incubation cabinet at approximately 24° C. anda relative atmospheric humidity of approximately 80% and a day/nightinterval of 12 h.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 10 ppm of activeingredient.

Ex_no. Eff. % 2 96

Example In Vivo Fusarium nivale (Var. Majus)-Test (Wheat)/Preventive

Solvent: 49 parts by weight of N,N-dimethylacetamide Emulsifier:  1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are slightly injuredby using a sandblast and afterwards they are sprayed with a conidiasuspension of Fusarium nivale (var. majus).

The plants are placed in the greenhouse under a translucent incubationcabinet at a temperature of approximately 10° C. and a relativeatmospheric humidity of approximately 100%.

The test is evaluated 5 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Ex_no. Eff. % 1 92 2 86

Experimental Examples Process (a)

5-fluoro-3-(difluoromethyl)-N-(5,5-dimethyl-5,6,7,8-tetrahydronaphthalen-1-yl)-1-methyl-1H-pyrazole-4-carboxamideExample 1

In a 25 ml round bottom flask, a solution of5,5-dimethyl-5,6,7,8-tetrahydronaphthalen-1-amine hydrochloride (200 mg,0.954 mmol, 1 eq.) in 5 ml of DCM is cooled to 0° C. and triethylamine(0.290 ml, 2.078 mmol, 2.2 eq) is added followed by DMAP (11 mg, 0.094mmol, 0.1 eq). A solution of5-fluoro-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride(220 mg, 1.039 mmol, 1.1 eq) in 1 ml of DCM is added dropwise. Stirringis allowed for 4 h at r.t. The reaction is quenched with 1N aq. HCl, anddiluted with EtOAc. The aqueous layer was separated and extracted withEtOAc. The organics were combined, washed with NaOH 1N, dried over MgSO4and concentrated. The crude material was purified by chromatography onsilica gel to give pure material (70%)

Process (b)

5-chloro-3-(difluoromethyl)-N-(6,6-dimethyl-5,6,7,8-tetrahydronaphthalen-1-yl)-1-methyl-1H-pyrazole-4-carbothioamideexample 33

In a microwave sealable tube, P₂S₅ (25 mg, 0.116 mmol, 0.5 eq) is addedto a solution of5-chloro-3-(difluoromethyl)-N-(6,6-dimethyl-5,6,7,8-tetrahydronaphthalen-1-yl)-1-methyl-1H-pyrazole-4-carboxamide(85 mg, 0.231 mmol, 1 eq) in 2 ml of dioxane. The tube is sealed and thereaction is microwaved 20 min at 130° C. The resulting solution isfiltered through alumina and washed with dioxane. The solvent isevaporated and the residue purified by chromatography on silica gel togive pure material (94%)

Process (c)

6,6-dimethyl-5,6,7,8-tetrahydronaphthalen-1-amine Example III-a-12

In a sealable reactor,5-bromo-2,2-dimethyl-1,2,3,4-tetrahydronaphthalene (1 eq) is dissolvedin 1,4-dioxane (15 ml for 250 mg of SM), tBu-carbamate (1.5 eq) is addedfollowed by XPHOS (0.1 eq) and cesium carbonate (2 eq). Argon is bubbledin solvent for 5 min and the reactor purged with Ar, Pd(OAc)₂ (0.05 eq)is added and the tube sealed. The reaction is heated at 100° C. untilLCMS indicate no starting material left. The reaction is diluted with EAand filtered through celite. Solvent is removed under vac. and theresidue dissolved in DCM. TFA (10 eq) is added. The reaction is refluxedfor 5 h, cooled and quenched with NaHCO₃ sat., extracted with EA. Driedover MgSO₄ and concentrated. The residue is purified on silica gel togive pure material.

Process (d)

5,5-dimethyl-5,6,7,8-tetrahydronaphthalen-1-amine Example III-a-1

1-(2-bromophenyl)-4-methylpentan-3-ol (17 g, 88.09 mmol) was added topolyphosphoric acid (170 g, 265.4 mmol). The mixture was heated to 130°C. for 20 minutes. The reaction progress was monitored by TLC (TLCsystem: 5% Ethyl acetate in hexanes, R_(f)=0.2). The reaction mass wascooled to room temperature, water (800 mL) was added and the mixture wasfurther cooled to 0° C. and the pH of the mixture was adjusted to 10-12using 50% solution of Sodium hydroxide. The mixture was extracted withEthyl acetate (3×600 mL) and the organic layer was concentrated todryness to obtain the crude product as a colorless oil (6.9 g, 49%)

1. A Compound according to formula (III-a)

wherein Q represents hydrogen; X represents fluorine; m represents 0 or1; R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independently from each otherrepresent hydrogen or methyl; wherein R⁷ and R⁸ can form the group═C(Y¹)Y² where Y¹ and Y² represent hydrogen or a group ═N—O—R^(c) whereR^(c) represents methyl or ethyl.
 2. A compound according to claim 1,wherein m is zero.
 3. A compound according to claim 1, wherein m is 1.4. A compound according to claim 1, wherein R⁷ and R⁸ form the group═C(Y¹)Y²
 5. A compound according to claim 1, wherein R⁷ and R⁸ form thegroup ═N—O—R^(c).
 6. A compound according to claim 1, wherein at leastone of R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ is methyl.
 7. A compoundaccording to claim 1, wherein at least two of R¹, R², R³, R⁴, R⁵, R⁶, R⁷and R⁸ are methyl.
 8. A compound according to claim 5, wherein R^(c)represents methyl.
 9. A compound according to claim 5, wherein R^(c)represents ethyl.